PROCESS FOR MAKING POLYPHENOLS FROM KETONES OR ALDEHYDES AND PHENOLS

Abstract: A catalyst useful for the condensation of an aldehyde or ketone starting material with a phenol is an insoluble mercaptosulfonic acid compound. The heterogeneous catalysts comprise catalytically-active species represented by formula (a). L is an optional linking group and is a bond, which catalytically active species is attached by the bond to an insoluble organic or inorganic support; or a catalytically-active species represented by formula (b), wherein L' is an optional linking group, is a bond and theta ' and theta '' are residues of theta , and a and b are independently selected from integers equal to or greater than 1.

Description: PROCESS FOR MAKING POLYPHENOLS FROM KETONES OR ALDEHYDES AND PHENOLS This invention relates to preparation of polyphenols, more particularly to the preparation of polyphenols from ketones or aldehydes and phenols. Acid-catalyzed condensation of phenols with aldehydes or ketones is well known. Acid catalysts include acidic ion exchange resin catalysts and soluble acid catalysts . Soluble acid catalysts can be, for example, hydrogen chloride, sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, nitric acid, dimethyl sulfate, sulfur dioxide, 4-toluenesulfonic acid, boron trifluoride, alkanesulfonic acids, boron trifluoride complexes and other acid-acting compounds, including compounds which are hydrolyzed by water to form acids, for example aluminum chloride, sulfonyl chloride and phosgene. A number of compounds are known to promote such an acid-catalyzed condensation. These promoters include mercaptan groups which are either free or bound to a resin. Alkyl mercaptans and bis-mercaptoethanolamine are examples of reported promoters. It has been proposed by Scriabine et al . (U. S. Patent 2,923,744) to produce Bisphenol A using sulfuric acid, promoted by mercaptoalkanesulfonic acids or salts or corresponding sulfonate esters at a level of 0.1-5 percent by weight of the base charge, to catalyze condensation of acetone and phenols, when used in amounts of 0.1 to 5 percent by weight based on total charge. Sulfuric acid is used in amounts of 2 moles per mole of acetone. Riemann et al. (U.S. Patent 4,675,458) have proposed making 9, 9-bis- (4-hydroxyphenyl) fluorene (BHPF) in the presence of sulfuric acid, preferably concentrated sulfuric acid, and a mercaptan, particularly 3- mercaptopropionic acid, as promoter. Massirio et al. (U.S. Patent 5,248,838) have disclosed the use of a combination of methanesulfonic acid and a mercaptan/mercaptoalkanoic acid for catalyzing the condensation of phenols with fluorenone. High levels of methanesulfonic acid with respect to the feed and the mercaptan/mercaptoalkanoic acid, are used. The reactions can be run in halogenated hydrocarbon solvents . Bottenbruch et al. (U. S. Patent 4,996,373) have proposed a process for producing dihydroxyaryl compounds from carbonyl compounds and phenols under high pressure, in the presence of various catalysts, including sulfonic acid resins. Catalysts containing sulfhydryl functionality, for example ion exchangers treated with mercapto compounds, have been disclosed for this use. Meyer et al. (U.S. Patent 4,387,251) have proposed processes for making 4,4 ' -dihydroxydiphenyl alkanes using aromatic sulfonic acids as condensing agents. Mercapto groups are included within the definition of R 3 and are characterized as being inert. Freitag et al . (5,210,328) disclose using the same types of sulfonic acid catalysts for making cycloalkylidene bisphenols. Jansen (U.S. Patent 2,468,982) has proposed preparation of bisphenols using anhydrous hydrogen chloride in combination with a mercaptoalkanoic acid, which may be formed in situ by reaction of a mercaptol with the ketone, as condensing agent. Knebel et al. (U.S. Patent 4,931,594) disclose the use of large amounts of sulfonic acid resin, mixed with uncombined 3-mercaptopropionic acid, to cause the condensation to occur. It has been proposed in British Patent 1,185,223 to use a mixture of insoluble resins, one a sulfonic acid resin and the other a resin containing mercapto groups, for making bisphenols. Randolph et al. (U.S. Patent 5,212,206) disclose a catalyst, made by treating a sulfonated ion-exchange resin with a dialkylamino ercaptan. Other references, representative of references on modification of sulfonic acid ion-exchange resins, include Wagner (U.S. Patent 3,172,916) . McNutt et al . (U.S. Patent 3,394,089) , Faler et al. (U.S. Patents 4,455,409; 4,294,995 and 4,396,728) ; Heydenrich et al . (U.S. Patent 4,369,293) ; Berg et al. (U.S. Patent 5,302,774) and Maki et al. (U.S. Patent 4,423,252) . The reactive catalysts generally include mercapto-functions attached to a sulfonic acid group in the form of a sulfonamido or ammonium sulfonate salt. Shaw (U.S. Patent 4,859,803) discloses preparing bis- phenols from phenol and a ketone in the presence of an acidic (sulfonic acid) ion-exchange resin and a mercaptan, the mercaptan being added at particular locations of a specified reactor configuration to prevent the formation of cyclic dimers. Li has disclosed (U. S. Patent 4,825,010) isomerization of by-products of condensates of phenols and ketones, using a catalytic amount of acidic sulfonated cationic-exchange resin having sulfonic acid sites ionically bonded to alkyl ercaptoamines. Other patents by Li (U.S. Patents 4,822,923 and 5,001,281) further suggest the state of the art of using ion-exchange resins to isomerize by-products of bisphenol syntheses. Powell et al. (U.S. Patent 5,105,026) disclose using acidic ion-exchange resins to isomerize undesirable products of bisphenol synthesis to desirable products, for example to Bisphenol A. Morgan (U.S. Patent 3,546,165) has disclosed condensation of phenol with various ketones, including fluorenone and indanone, using high levels of hydrochloric acid or hydrogen chloride, in the presence of minor amounts of 3-mercapto-propionic acid. The products are used for the preparation of polyester resins. Szabolcs (U.S. Patents 4,467,122 and 4,503,266) discloses washing crude product, containing BHPF, from a hydrochloric acid/zinc chloride catalyzed process, to remove HCl, ZnCl 2 and excess phenol, prior to recrystallization from dichloroethane. See also the abstract for DE OLS 2,948,222 (7/30/81) . Korshak et al. (SU 172,775) disclose washing a mixture of phenol, BHPF and HCl with water, after which phenol is removed by distillation. The following references, herein incorporated by reference, disclose the preparation of resins, containing sulfonic acid functionality, introduced either by copolymerization or by sulfonation after polymerization: U.S. Patent 3,205,285 Turbak et al. U.S. Patent 3,366,711 Mazzolini et al. U.S. Patent 3,426,104 Masson U.S. Patent 4,587,304 Thaler et al. U.S. Patent 4,764,557 Eichenauer et al. Trapasso (U.S. Patent 3,706,707) discloses the preparation of adducts from a polymerized cyclic ether and a sultone. Dean (U.S. Patent 4,568,724) is of similar interest with respect to reaction products from an EPDM rubber and a sultone. Welch (U.S. Patent 3,029,221) and Niwa et al. (U.S. Patent 4,912,170) disclose processes for modifying polystyrene resins. It is an object of this invention to provide a process for the condensation of aldehydes or ketones with phenols, to achieve high yields of preferred bis- (4- hydroxyaryl) isomers with low reaction times while avoiding use of strong inorganic acids. Further objects of the invention include the development of processes for the synthesis of polyphenols, characterized by high yields of high purity products under reaction conditions, which are not corrosive to vessels in which the processes are conducted. In addition, avoiding the use of sulfuric acid, eliminates the possibility of side reactions, including sulfonation of phenols. In one aspect, this invention relates to a process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in at least one position, comprising reacting the aldehyde or ketone starting material with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material; provided that the soluble mercaptosulfonic acid compound is characterized by the formula (HS) a -θ-(S0 3 H) b wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b are independently selected from integers from 1 to 20; and the insoluble mercaptosulfonic acid comprises a catalytically-active species represented by the formula (HS) a -θ'-(S0 3 H) b (a) t in which θ 1 is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from l to 20; L is an optional linking group and - is a bond, which catalytically-active species is attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by the unit formula (HS). (S0 3 H) b \ / -[ θ n - L']- (b) wherein θ" is an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to 20; L 1 is an optional linking group and - is a bond. This invention further relates to novel catalytically-active polystyrene resins, characterized by bearing at least one of each of a mercapto function and a sulfonic acid function on some individual styrene units of a polymer chain. In yet another aspect, this invention relates to processes for preparing the catalytically-active pol¬ ystyrene resins. These processes preferably comprise steps of (b) sulfonating a haloalkylpolystyrene to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to corresponding alkali metal salts; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a corresponding mercapto group or precursor thereof,-(e) optionally hydrolyzing the thus-thiolated intermediate with an acid or base when the thiolated group so requires and (f) optionally acidifying (if so required) to produce sulfonic acid functional groups units. The process of the invention permits use of very low levels of a single acidic condensing agent. The process permits simplified product isolation procedures, recycle procedures, and/or waste management. The process does not require a neutralization step to remove hydrochloric or sulfuric acid and does not produce a waste salt stream. The acidic condensing agents used in the process of this invention are readily removed from the reaction mixtures and can be recovered and recycled. The process of this invention results in high selectivity toward preferred bis- (4-hydroxyaryl) isomers and very fast reaction rates. The process of this invention is particularly useful for the preparation of bis (hydroxyary1) compounds, such as bisphenol A and , 9-bis- (4-hydroxyphenyl) fluorene, both of which are useful in the preparation of polycarbonates and other commercially significant polymers. The heterogeneous catalysts disclosed herein advantageously are more reactive than heterogeneous catalysts currently used. They advantageously allow using lower temperatures with correspondingly greater selectivity for desired product than is currently experienced. Greater selectivity reduces purification necessary to produce a desired or preselected purity of product. Thus for a commercially produced bisphenol like Bisphenol A, a heterogeneous catalyst disclosed herein can be advantageously substituted in an existing commercial process, run with the same or higher throughput at a lower temperature with less purification to achieve at least equally pure product. Ketones or aldehydes and phenolic compounds (hereinafter phenol, phenols, a phenol or phenolic starting material) useful in process of the invention are known in the art and are described in the literature, for instance Jansen '982, supr . Maki et al. , '252, supra , Morgan '165, supra , and Knebel et al. '594, supra, all of which are herein incorporated by reference. The condensations of this invention can be represented by the equation for a representative condensation, that of phenol with 9-fluorenone: HO OH The process for making bisphenol A can be represented by the equation: Phenol starting materials are advantageously any aromatic hydroxy compounds which have at least one unsubstituted position, and optionally have one or more inert substituents such as hydrocarbyl or halogen at the one or more ring positions. An inert substituent is a substituent which does not interfere undesirably with the condensation of the phenol and ketone or aldehyde and which is not, itself, catalytic. Preferably, the phenols are unsubstituted in the position, para to the hydroxyl group. Alkylene (alk) , alkyl, cycloaliphatic, aryl, arylene (ar) , alkylarylene (alkar) , arylalkylene (aralk) , alkylcycloaliphatic and alkylenecycloaliphatic are hydrocarbyl functions, that is, functions containing carbon and hydrogen atoms. The alkylene functions can be straight or branched chain and saturated or unsaturated, that is alkylene, alkenylene, or alkynylene. Cycloaliphatic hydrocarbon residues include both saturated and unsaturated cyclic residues, that is, cycloalkylene and cycloalkenylene. Arylene includes mono- and polycyclic aromatic residues, for example those of benzene, biphenyl, biaryl, naphthyl, phenanthrenyl, anthracenyl or aryl groups, including those bridged by an alkylene group. Alkaryl residues include alkyl, alkenyl and alkynyl-substituted aromatic rings. Aralkyl includes alkyl, alkenyl or alkynyl residues, substituted by one or more aromatic groups. Alkyl groups include both straight- and branched- chain isomers of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, nonadecyl and eicosyl groups, as well as the corresponding unsaturated (alkenyl or alkynyl) groups, as well as higher homologues. Preferably, the alkyl groups are of 1-20 carbon atoms, more preferably of 1-5 carbon atoms, most preferably those of 1-3 carbon atoms. Alkyl of 1-5 carbon atoms includes the various methyl, ethyl, propyl, butyl and pentyl isomers. Alkyl, aryl, alkaryl and aralkyl substituents are suitable hydrocarbyl substituents on the phenol reactant. Other inert substituents on the phenols include, but are not limited to alkoxy, aryloxy or alkaryloxy, wherein alkoxy includes methoxy, ethoxy, propyloxy, butoxy, pentoxy, hexoxy, heptoxy, octyloxy, nonyloxy, decyloxy and polyoxyethylene, as well as higher homologues; aryloxy, phenoxy, biphenoxy, naphthyloxy, etc. and alkaryloxy includes alkyl, alkenyl and alkylnyl-substituted phenolics. Additional inert substituents on phenols include halo, such as bromo, chloro or iodo. Cyano and nitro substituents may deactivate the phenols and aldehyde and carboxylic acid substituents may cause interfering reactions. Additional hydroxyl substituents may be suitable in some cases. Preferred substituents include alkyl moieties containing from 1 to 10 carbon atoms, more preferably, lower alkyl moieties, containing from 1 to 5 carbon atoms, most preferably from 1 to 3 carbon atoms. The alkyl substituents may be straight or branched chain isomers. Exemplary phenols include, but are not limited to, phenol, 2-cresol, 3-cresol, 4-cresol, 2-chlorophenol, 3-- chlorophenol, 4-chlorophenol, 2-tert-butylphenol, 2,4- dimethylphenol, 2-ethyl-6-methylphenol, 2-bromophenol, 2- fluorophenol, 2-phenoxyphenol, 3-methoxyphenol, 2,3,6- trimethylphenol, 2, 3, 5, 6-tetramethylphenol, 2,6-xylenol, 2, 6-dichlorophenol, 3, 5-diethylphenol, 2-benzylphenol, 2, 6-di-tertbutylphenol, 2-phenylphenol, 1-naphthol, 2- naphthol and the like. Preferred phenols include phenol, 2- or 3-cresol, 2, 6-dimethylphenol, resorcinol, naphthols, and mixtures thereof. Most preferably, the phenol is unsubstituted. The ketones which are advantageously used include any ketone having a single ketone carbonyl (C=0) group or several ketone carbonyl groups, and which are reactive under the conditions used. The ketones can be substituted with substituents, which are inert under the conditions used. Inert substituents are as set forth above for the reactive phenols. The ketones are advantageously selected from aliphatic, aromatic, alicyclic or mixed aromatic-aliphatic ketones, diketones or polyketones . , of which acetone, methyl ethyl ketone, diethyl ketone, benzil, acetylacetone, methyl isopropyl ketone, methyl isobutyl ketone, acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5- trimethylcyclohexanone, anthraquinone, 4- hydroxyacetophenone, acenaphthenequinone, quinone, benzoylacetone and diacetyl are representative examples. Ketones having halo, nitrile or nitro substituents can also be used, for example, 1, 3-dichloroacetone or hexafluoroacetone. Aliphatic ketones which are useful starting materials include, but are not limited to acetone, ethyl methyl ketone, isobutyl methyl ketone, 1, 3-dichloroacetone, hexafluoroacetone and the like. A preferred aliphatic ketone is acetone, which condenses with phenol to produce 2, 2-bis- (4-hydroxyphenyl) -propane, commonly known as bisphenol A. Another preferred aliphatic ketone is hexafluoroacetone, which reacts with two moles of phenol to produce 2,2-bis- (4-hydroxyphenyl) -hexafluoropropane (bisphenol AF) . A preferred class of ketones has at least one hydro- carbyl group containing an aryl group, for example, a phenyl, tolyl, naphthyl, xylyl or 4-hydroxyphenyl group. Other preferred ketones include those in which the hydrocarbon radicals connected to the carbonyl groups of the ketone is in a cycloaliphatic group. Examples of spe- cific preferred ketones include 9-fluorenone, cyclohexanone, 3,3, 5-trimethylcyclohexanone, indanone, indenone, anthraquinone and the like. Most preferred ketones include 9-fluorenone, benzophenone, acetone, acetophenone, 4-hydroxyacetophenone and 4,4 ' -dihydroxybenzophenone. Most preferably, the process of this invention is used to make bisphenol A by reaction of phenol with acetone or to make 9,9-biε-(4- hydroxyphenyl) fluorene (BHPF) by reaction of phenol with 9-fluorenone. The process of this invention can also be used for the condensation of phenols with aldehydes, for example, with formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or higher homologues of the formula RCHO, wherein R is alkyl of 1-20 carbon atoms. The condensation of two moles of phenol with one mole of formaldehyde produces bis- (4-hydroxyphenyl)methane, also known as Bisphenol F. It will be understood that dialdehydes and ketoaldehdyes, for example, glyoxal, phenylglyoxal or pyruvic aldehyde, can also be used. The products are generally geminal bisphenols, that is, compounds having one or more single carbon atoms to which are attached nuclei of two phenolic moieties. This single carbon atom corresponds to the carbonyl carbon of the ketone or aldehyde reactant. In the case of starting materials, containing more than one aldehyde or ketone carbonyl, the product will contain more than one geminal bisphenolic moiety. For example, the condensate from acetyl acetone and phenol is 2,2,4,4-tetrakis- (hydroxyphenyl)pentane and the condensate from benzoylacetone is 2,2,4,4-tetrakis- (hydroxyphenyl) -4- phenylbutane. The mercaptosulfonic acid catalyst is any species, whether soluble or insoluble in the reaction mixture, containing at least one thiol (SH) group and at least one sulfonic acid (S0 3 H) group, including any group which can be converted to a sulfonic acid group under the reaction conditions used. In the specification and claims, the soluble mercaptosulfonic acid moiety is represented by the formula (HS) a -θ-(S0 3 H) b wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and each of a and b is independently an integer from 1 to 20. "Soluble mercaptosulfonic acid, " as used in the specification and claims, means a compound which has some solubility in the reaction mixture and which can be removed from the mixture, at the end of the reaction, by extraction, ion-exchange, precipitation, absorption, etc. "Insoluble mercaptosulfonic acid," as used in the specification and claims, means a material, which is insoluble in the reaction mixture. These materials are generally polymeric organic resins, or catalytically- active compounds, bonded to an inorganic support. When θ is alkylene, the alkylene can be of 2 to up to 20 carbon atoms, including straight and branched chain alkylene moieties, corresponding heterochain moieties and alkylene substituted with inert substituents. Inert substituents include, for example, alkoxy, alkenyl, alkynyl, halo, nitro, aryl, etc. Representative mercaptoalkanesulfonic acids include, but are not limited to, 2-mercaptoethanesulfonic acid, 3- mercaptopropanesulfonic acid (MPSA) , 4-mercaptobutanesulfonic acid (MBSA) , 4-mercaptopentane- sulfonic acid, 3-mercapto-2, 2-dimethylpropanesulfonic acid, 2,3-dimercaptopropanesulfonic acid, mercaptopropane- 2,3-disulfonic acid, 2-benzyl-4-mercaptobutanesulfonic acid, 5-mercaptopentaneεulfonic acid or the like. Most preferred among this group of catalysts are 3- mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acids. The types of mercaptoalkanesulfonic acids which are useable are exemplified by the following compounds of Formula I : HS S0 3 H Formula 1(a) Formula 1(b) SH Formula 1(c) wherein Q is an inert substituent and Y is an optional hetero element, for example 0, N-Q or S. Q is H, hyd¬ rocarbyl, halo, carboxy, sulfonyl, etc., as described above for inert substituents on the phenol, ketone or aldehyde starting materials. More than one Q may optionally be present. The Q substituent can be at any position on the chain and more than one Q can be present . As set forth in the general formula for the soluble catalysts, more than one SH or sulfonic acid function are optionally present in the catalyst. Compounds of Formula I (a) are included within the generic formula HS(CH 2 ) y CH(Q) (CH 2 ) x S0 3 H wherein y is an integer from 0 to 20, z is an integer from 0 to 20, Q is an optional inert substituent and y + z > 1 , up to a maximum of 40. Compounds of Formula I (b) are included within the generic formula HS(CH 2 ) y -Y- (CH 2 ) z S0 3 H, wherein one or more inert substituents, Q, can be attached at any point along the carbon chain; wherein Y is a heteroelement, for example -S-; each of y and z is at least 1 and y + z > 2, up to a maximum of 40. Preferred linear mercaptoalkanesulfonic acids are those in which the distance between the mercapto and sulfonic acid functions are less than 20 atoms, including both carbon and heteroato s. Compounds of Formula 1(b) can also have more than one SH and/or more than one sulfonic acid function. Compounds of Formula I (c) are included within the formula HS ? H(CH 2 ) y + z S0 3 H Q wherein y and z are as above. Mercaptosulfonic acid precursors can also be used as catalysts, by conversion to active mercaptosulfonic acid catalysts in the reaction mixtures. For example, a precursor alkali metal sulfonate salt can be neutralized with a mineral acid to produce a free sulfonic acid. Sulfonate ester precursors can be hydrolyzed by treatment with a strong base, for example sodium or potassium hydroxide, and thus converted to a corresponding alkali metal salt. A further precursor of sulfonic acids for the practice of this invention, is a sulfonyl halide group, which can readily converted to a corresponding sulfonic acid. Mercaptosulfonic acids can be prepared from corresponding haloalkanesulfonic acids by reaction with an alkali metal mercaptide, for example, X-alk-S0 3 H + NaSH → HS-alk-S0 3 H + NaX wherein X is Cl, Br or I and alk is alkylene, generally in accordance with Ellis et al. , "The Preparation and Properties of a Double Series of Aliphatic Mercaptans," J. Am. Chem. Soc.. vol. 54 (1932), pages 1674-1687. Alternatively, treatment of a haloalkanesulfonic acid with an alkali metal thioacetate, followed by hydrolysis, can be used to prepare mercaptoalkanesulfonic acids. Another route to mercaptosulfonic acids is by converting halides to a corresponding thiouronium salt, which is hydrolyzed with a strong base, as follows: X-alk-S0 3 H + H 2 NCSNH 2 → HN=C-S-alk-S0 3 H I NH 2 -HX I NaOH HS-alk-S0 3 H generally according to Schramm et al . , "The Synthesis of mercaptoalkanesulfonic Acids," J. Am. Chem. Soc. f vol. 77 (1955), pages 6231-6233. Hydroxyalkanesulfonic acids can also be converted to the corresponding mercaptoalkanesulfonic acid by reaction with thiourea and HBr/HCl to produce a thiouronium salt, which is hydrolyzed using a strong base. See, Frank et al., "The Preparation of Mercaptans from Alcohols," J. Am. Chem. Sπc.. vol. 67 (1946), pages 2103-2104. Higher mercaptoalkanesulfonic acids can be prepared from higher olefinsulfonic acids, for example oleylsulfonic acid, by adding hydrogen sulfide across the olefinic bond. Alternatively, the olefinic bond of an olefinic sulfonic acid can be halogenated, for example chlorinated, and the halogen moiety replaced by a mercapto function, as above. Mercaptoalkanesulfonic acids can also be made from corresponding sultones, e.g., 1,4-butanesultone, in accordance with Chem. Abs.. 90:86742m (1979) ; R. Fischer, "Propanesultone, " Ind. Eng. Chem. r vol. 56 (1964), pages 41-45; or A. Mustafa, "The Chemistry of Sultones and Sultams," Chemical Reviews, vol. 54 (1954), pages 195-223. When -θ- is arylene, the sulfonic acid and mercapto moieties are attached directly to an aromatic ring. Representative aromatic mercaptosulfonic acids include 2- ercaptobenzenesulfonic acid, 3-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid, 2- mercaptonaphthalenesulfonic acid or the like. The aromatic residues can be substituted with substituents, e.g., H, alkyl, alkenyl, alkynyl, aryl, halo, alkoxy, aryloxy (Q, above) , which are inert under the reaction conditions. The active catalysts can contain more than one SH and/or more than one sulfonic acid function in each molecule. Cycloaliphatic residues include those of cyclohexane, cyclopentane and cycloheptane; the aliphatic ring of indane, tetralin or benzocycloheptane, and the like. Representative cycloaliphatic mercaptosulfonic acids include, but are not limited to, 2- mercaptocyclohexanesulfonic acid, 2-mercaptocyclo- pentanesulfonic acid, 3-mercaptocyclohexanesulfonic acid, 3-mercaptocyclopentanesulfonic acid and the like. The cycloaliphatic rings can also be substituted with inert substituents and can contain more than one SH group and/or more than one sulfonic acid group. Representative alkylenecycloaliphatic mercaptosulfonic acid compounds can be represented by the following formulas: C,H 2z S0 3 H wherein y and z are integers of 0 to 20; Q is an optional inert substituent selected from alkyl, aryl, halo, alkoxy or aryloxy and y + z > 1. Typical compounds include (mercaptomethyl) cyclohexanesulfonic acid and (mercaptomethyl) (sulfomethyl)cyclohexane. Typical alkylenearyl mercaptosulfonic acids can be represented by the formulas: Q C ι H 2 zS 0 3 H wherein x, y and Q are as above and x + y > 1. A typical compound of this group, (mercaptomethyl)benzene-sulfonic acid, can be prepared from a corresponding chloromethyl- or bromo- methylbenzenesulfonic acid. Oligomers from vinylsulfonic acid can provide soluble materials, containing large numbers of mercapto and sulfonic acid groups. This type of soluble catalyst can be prepared from oligomers containing vinylsulfonic acid units, half of which can be converted to chlorosulfonyl units and reduced to mercapto units in accordance with the following reaction scheme: - [-CH 2 -CH-CH 2 -CH-CH 2 -CH-CH 2 -CH-] - - [-CH, - [-CH 2 -C CHH--CCHH 22 --CCHH--CCHH 22 --CCHJ-CH 2 -CH-] SO 3 H SH S0 3 H SH Another type of oligomeric catalysts, containing a multiplicity of mercapto and sulfonic acid units, can be prepared from propenesultone. Propenesultone is prepared as described by G. Manecke et al., Che . Abs. 53:2083c (1959) , Helberger et al., DE 1,146,870 and Chem. Abs. 59:11259 (1963) . The sultone ring of the polymer can be opened, generally as above, to furnish mercaptosulfonic acid oligomers, containing a plurality of mercapto and sulfonic acid units. In addition, oligomers containing a plurality of mercaptosulfonic acid functions can be prepared from oligomers of 4-allyl-l,4-butanesultone. The monomer is prepared as described for 4-benzyl-1,4-butanesultone, using allyl chloride instead of benzyl chloride. 4,4- Diallyl-l,4-butanesultone can be prepared by addition of a second allyl group. Other catalytically active mercaptosulfonic acid oligomers can be prepared from allyl vinylsulfonate (CH=CHS0 2 OCH 2 CH=CH 2 ) , which is polymerized to form a corresponding sultone-containing polymer in accordance with E. Goethals, "Synthesis and Polymerization of Allyl Vinyl Sulfonate," Polymer Letters, vol. 4 (1966), pages 691-693. The resulting polymer, containing sultone groups is treated with a reactive thiolate to open the sultone rings and produce mercaptoalkyl sulfonate polymers. The conversions can be represented by the equation; Similar catalytically-active solid oligomers can be prepared from oligomers of allyl allylsulfonate (CH 2 =CHCH 2 S0 2 OCH 2 CH=CH 2 ) , which can be polymerized in accordance with E. Goethals et al. , "Polymerization and Copolymerization of Allyl Allyl Sulfonate, " J. Macro ol. Sci . - Chem.. vol. A5 (1971), pages 63-72. The oligomers are converted to mercaptosulfonic acid functional materials by a corresponding ring opening reaction. The conversion can be represented by the equation: Heterocyclic residues advantageously include cyclic residues, containing N, 0, or S. These will generally correspond to aromatic compounds, for example, residues from pyridine, thiophene, quinoline, phenanthridine, and the like, as well the corresponding partially or fully hydrogenated compounds. Alkyleneheterocyclic residues otherwise correspond to aromatic residues of the same configuration, as do alkyl heterocyclic residues, as well as corresponding fully or partially hydrogenated compounds . Preferred soluble mercaptosulfonic acids are compounds in which the mercaptan and sulfonic acid functions are separated by a chain of 2 to 10 atoms, whether the chain or linker arm is in an alkylene group or incorporated in an aromatic, cycloaliphatic or heterocyclic ring, whether or not the chain includes heteroelements, and whether or not the mercapto and sulfonic acid functions are attached directly or indirectly to the ring structures. Preferred soluble catalysts for the practice of this invention are mercaptosulfonic acids in which a and b are independently 1 from to 4. More preferably, a and b are independently 1 or 2. Most preferred are mercaptosulfonic acids, contain¬ ing mercapto and sulfonic acid functions in a 1:1 molar ratio, that is a and b are each 1, more particularly 3- mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acid. When the mercaptosulfonic acid is insoluble, the heterogeneous catalyst comprises a catalytically-active species represented by Formula II: (HS) a -θ' - (SO,H) h Formula II t in which each of a and b is independently an integer from 1 to 20, θ' is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue, L is an optional linking group and - is a bond, which catalytically-active species is attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by Formula III : (HS). (S0 3 H) b \ / - [ Θ M - L-] - Formula II wherein θ" is an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to 20; L 1 is an optional linking group and - is a bond. Catalytically-active materials of Formula II are generally derived from polymers of ethylenic monomers, wherein the insoluble organic support is the main chain of a resulting polymer and -L- is a covalent bond or a linking group. This type of polymer will include unit structures represented by the general formula - [CH j CH] - t (HS) a -θ'-(S0 3 H) b . Preferably, the catalytically-active materials will include those having from 1 to 4 of each of mercapto and sulfonic acid groups per θ' . More preferably, the catalytically-active materials will include those having 1 or 2 of each of mercapto and sulfonic acid groups per θ * . Most preferably, the catalytically-active materials contain 1:1 ratios of mercapto and sulfonic acid functions and will correspond to the general formula - [CH 2 CH] - HS-θ'-S0 3 H. Exemplary polymers, made from ethylenically unsaturated monomers and which can be used as carriers for the catalytically-active species, include, but are not limited to: Q± Monomer (s) phenyl styrene -CH 2 - phenyl allylbenzene -O- phenyl phenyl vinyl ether -COO- alkyl, aryl acrylic esters -OCO- alkyl, aryl vinyl esters -(CH 2 ) r - alkenyl α,ω-diolefins r = 4-20 -NH- alkyl, aryl vinylamines -CONH- alkyl, aryl acrylamides -NHCOO- alkyl, aryl vinylurethanes alkylphenyl vinyltoluene phenyl α-methylstyrene -S- phenyl phenyl vinyl ether -S0 2 - aryl vinyl aryl sulfones -SO- aryl vinyl aryl sulfoxides -NS0 2 - aryl aryl sulfonamide The linking groups, -L-, can accordingly include alkylene, a covalent bond, oxycarbonyl, carbonyloxy, oxy, ureido, amido, amino, thio (sulfur), sulfono or sulfoxo. Preferred linking groups include a covalent bond, methylene, sulfur or oxygen, more particularly a covalent bond joining a phenyl ring to a carbon backbone in polystyrene or polystyrene derivatives, containing each of SH and S0 3 H functions in single monomeric units of polystyrene. One type of novel catalytically-active polystyrene resins, includes unit structures represented by Formula IV CRS0 3 H Formula IV CnH 2n CHR SH wherein B is a bridging group , R and R 1 are independently selected from H, alkyl or aryl, -C n H 2n - is straight or branched chain alkylene and n is an integer from 0 to 20. The bridging group B, can be selected from alkylene, generally as above. Alkyl and aryl are defined above. Polystyrene resins of Formula IV can be made by the steps of (a) reacting a haloalkystyrene polymer with a lithiated sultone, (b) treating a resulting sultone-func- tionalized polymer with a reactive thiolate and (c) acidifying the resulting intermediate to produce a polymer containing (mercaptosulfoalkyl) styrene units. Haloalkylstyrene polymers include, but are not limited to poly(chloromethylstyrene) , poly(bromomethylstyrene) , poly(bromopropylstyrene) , poly(bromopentyl) styrene or the like. including homopolymers and copolymers, whether made by polymerization of haloalkylstyrene monomers or haloalkylation of polystyrene resins. Representative starting materials can be made by copolymerization of vinylbenzyl chloride or vinylbenzyl bromide with styrene. Either starting material can be crosslinked with divinylbenzene or similar crosslinking monomers. The polymers can contain other monomers, e.g., styrene, α- methylstyrene, acrylonitrile, butadiene, maleic anhydride, ethylene or propylene. The haloalkylated polymers will advantageously contain from 0.5 meq/g to 10 meq/g of halomethyl groups. Halomethylated or haloalkylated polymers normally comprise mixtures of polymers, substituted in the ortho-, meta- and para-positions. Poly(chloromethylstyrene) , containing 2-5 meq/g of chlorine, is a preferred starting material. The reaction sequence described above can be performed utilizing a variety of chloromethylated or bromomethylated styrene polymers or copolymers. In particular, crosslinked halomethylated sty- rene/divinylbenzene co-polymers in various forms, for example microporous or macroporous beads, powders, etc., can be functionalized to provide the corresponding mercaptosulfonic acid polymers. In the case of all the polymer based catalysts utilization of the functionalized styrene or other polymers in bead form may advantageously simplify workup procedures during preparation and provide for more facile implementation in catalyst applications. Beads are suitably of any size through which effective flow and contact is achieved. Physical forms including powders, beads, extruded shapes, macroporous and microporous configuration are, however, suitably used in the practice of the invention. In general smaller size provides more surface area for contact, but larger size permits greater flow through a bed. Optimizing these factors is within the skill in the art. Reactive thiolates advantageously include, but are not limited to, sodium thioacetate, potassium thioacetate, ammonium thioacetate and lithium thioacetate and the corresponding hydrosulfides. Of these, lithium, sodium or potassium thioacetate is preferred. When conversion to a mercapto function is done through a thiourea intermediate, the thioureas are advantageously selected from thiourea, N-methylthiourea, N-ethylthiourea, N-phenylthiourea or the like. In another alternative procedure, sodium thiosulfate can be used. A preferred species of catalytically-active polystyrene resin is made by reacting poly(chloromethyl) styrene with lithiated 1,4-butanesultone to produce an intermediate sultone, represented by the structural unit formula: CHS0 2 0 (CH 2 ) 2 CH 2 The resulting polymer contains (ε-mercapto-β-sulfo- pentyl) styrene units, that is, n in Formula IV is 2 and B is -CH,-. Most preferably, this type- of resin is made from a slightly crosslinked polystyrene; the resulting catalytically active material is designated as PMBSA-MER. Another type of catalytically-active polystyrene resins can be prepared by the steps of: (a) alkylating a polystyrene with an alkenyl halide of the formula RC(R 1 ) =C<R 2 ) C m H 2m CH(R 3 )X, wherein each of R, R 1 , R 2 and R 3 is H, alkyl or aryl; m is 0 to 20 and X is F, Cl, Br or I to produce a haloalkyl polystyrene; (b) sulfonating the resulting haloalkylpolystyrene to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to a sodium or potassium sulfonate function; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a corresponding mercapto function or precursor thereof and (e) optionally hydrolyzing the thus-thiolated intermediate with an acid or base when the thiolated group so requires; and (f) optionally acidifying (if so required) to produce the sulfonic acid function. This process can be represented broadly by the reaction sequence: (R )C = C(R )C__H 2 mCH(R )X H- C(R ) C B H 2 mCH(R )X C,H 2 aCH(R )X sulfonation C(R ) H C B H 2 .CH(R )X C»H 2 - B CH (R )X to produce intermediate haloalkyl sulfonated styrene polymers, of which halo functions are converted to mercapto functions to produce the following types of products of Formula V: C (R )H C n H 2 mCH(R ) SH C B H 2B CH (R ) SH Formula V Alkenyl halides optionally contain aryl and alkyl substituents, as defined above. Representative alkenyl halides, useful for preparing the catalytically-active polymers, include, but are not limited to, allyl chloride, allyl bromide, allyl iodide, methallyl chloride, methallyl bromide, crotyl chloride, crotyl bromide, 4-bromo-l- butene, 5-bromo-l-butene, 6-bromo-l-hexene or higher chloro or bromoalkenes. Preferably, the alkenyl halides are allylic halides, represented by the formula RC(R 1 )=C(R 2 )CH(R 3 )X. Most preferably, the alkenyl halide is 5-bromo-l-pentene, 11-bromo-l-undecene or allyl bromide. A particularly preferred product thus made can be characterized by the formula, in the case of a product from 5-bromo-l-pentene: SH or, when the halide is allyl bromide or allyl chloride, by the formula: CH 2 SH Reactive thiolates are as defined above. Most preferably, the reactive thiolate is an alkali metal thioacetate or hydrosulfide. By varying the choice of starting bromoalkene (or other haloalkene) used in the alkylation step of the process, the basic procedure described above can also be used to prepare a variety of catalysts with varying chain lengths between the mercaptan and sulfonic acid moieties. A number of catalysts with different amounts of mercaptosulfonic acid sites, depending upon the degree of functionalization in the alkylation and sulfonation steps in the process, and structural relationships between the mercaptan and sulfonic acid sites, depending upon the choice of bromo- or chloroalkylating agent, can accordingly be made. Preferred catalytically-active species of Formula V are those derived from polystyrenes, treated with 5-bromo- 1-pentene, 11-bromo-1-undecene or an allylic halide of the formula RCH=CH 2 CH 2 X, wherein R is H or alkyl of 1-5 carbon atoms. In another aspect, this invention relates to novel [(mercaptoalkyl) (sulfo)phenylalkyl] sulfonated polystyrene catalysts, made by a process comprising the steps of: (a) alkylating a haloalkylated polystyrene with a haloalkylarylene compound to produce an intermediate haloalkylpolystyrene having [ (haloalkyl)phenylalkyl] styrene units; (b) sulfonating the thus-produced haloalkylpolystyrene intermediate to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to corresponding alkali metal salts; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a corresponding mercapto function or precursor thereof and (e) optionally hydrolyzing the thus-thiolated intermediate with an acid or base when the thiolated group so requires; and (f) optionally acidifying (if so required) to produce the sulfonic acid function. This process produces polymers having repeating units of the formula: wherein n is preferably an integer from 0 to 10, more preferably 2 or 3. A representative member of this series of polymers, designated as DPMSA-XE3C is made from chloromethylstyrene polymer and 3-bromopropylbenzene, in accordance with the following reaction sequence: sulfonation 1 ) C I SO 3 H 2 ) NaHC0 3 thiolation 1) Na thioacetate 2) acid hydrolysis The haloalkyl polystyrene starting materials can advantageously be selected from chloromethylated polystyrenes, bromomethylated polystyrenes, chloroethylated polystyrenes, iodoethylated polystyrenes or the like, generally as above, preferably the halomethylated polystyrenes. Those skilled in the art recognize that selectivity decreases with haloalkyl groups on aryl rings which groups have similar selectivity. The haloalkylaryene compound can conveniently be selected from chlorobenzene, (chloromethyl) benzene, (chloroethyl)benzene, (chloropropyl)benzene, (chlorobutyl)benzene, as well as the corresponding fluoro, bromo and iodo analogues. Representative examples include (2-chloroethyl)benzene, (2-bromoethyl)benzene, (2- iodoethyl)benzene, l-chloro-3-phenylpropane, l-bromo-3- phenylpropane, and l-iodo-3-phenylpropane. The bromo compounds are preferred. The alkylation is conveniently carried out in the presence of a Friedel-Crafts catalyst, of which aluminum trichloride, aluminum bromide, boron trifluoride, hydrogen fluoride, phosphoric acid, zinc chloride, titanium chloride, ethylaluminum dichloride and stannic chloride are representative. A preferred catalyst is aluminum chloride in nitromethane or nitrobenzene, as disclosed by A. Warshawsky et al. , "Functionalization of Polystyrene. I . Alkylation with Substituted Benzyl Halide and Benzyl Alcohol Compounds," J. Org. Chem.. vol. 43 (1978), pages 3151-3157. Conveniently, after alkylation, unreacted haloalkylbenzene, solvent and catalyst in admixture are removed from the alkylated polystyrene by means within the art such as filtration. Advantageously, the admixture is recycled for reaction with additional haloalkyl polystyrene. The alkylated polystyrene is optionally washed with a solvent such as dichloromethane and optionally dried. The resulting alkylated polystyrene is sulfonated using chlorosulfonic acid, oleum or other known sulfonating agents. Prior to conversion of the halo moiety to the mercapto moiety, it is convenient to convert the sulfo moieties to corresponding alkali metal salts. Chlorosulfonic acid, sulfuric acid or sulfur trioxide is conveniently used in an amount sufficient to achieve a predetermiend or desirable degree of sulfonation, advantageoulsy to avoid unnecessary workup, in an amount not in large excess of the sufficient amount which varies with each resin but is determined without undue experimentation. The advantages of lower reaction temperatures are greater with chlorosulfonic acid. The thiolating reagents are conveniently selected from those disclosed above. Sodium thioacetate is preferred. Excess sodium hydrosulfide is optionally used for thiolation. Hydrolysis is then unnecessary since a thio group rather than a thioacetate is formed. The intermediate thiolated compound is, if necessary, acidified with a strong acid to convert sulfonate salt moieties to corresponding sulfonic acid moieties. Advantageously, a mineral acid is used, as above. In an alternate embodiment, the process comprises : (a) alkylating a polystyrene resin with a halomethyl haloalkylarylene compound to produce an intermediate having [ (haloalkyl)phenylalkyl] styrene units, (b) sulfonating the thus-produced intermediate to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functions to corresponding alkali metal salts; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a corresponding mercapto function or precursor thereof and (e) optionally hydrolyzing the thus-thiolated intermediate with an acid or base when the thiolated group so requires; and (f) optionally acidifying (if so required) to produce the sulfonic acid function. Illustrative of this reaction is the following sequence The alkylating step is performed as in the preceeding process optionally in a solvent such as chloroform, 1,2- dichloroethane, dichloromethane, 1,2-dichloropropane, preferably a solvent which swells polystyrene (for example styrene/divinylbenzene copolymer beads) . The alkylating agent is any halomethyl haloalkylarylene preferably wherein the alkyl group has from 0 to 10 carbon atoms. The arylene group preferably has from 6 to 14 carbon atoms. It is within the skill in the art to select halomethyl haloalkylarylenes in which the haloalkyl and halomethyl groups have activities sufficiently different to achieve the desired result. Representative halomethyl haloalkylarylene compounds include (2-bromoethyl)benzylchloride and (3- bromopropyDbenzylchloride. Chloromethyl haloalkylarlenes are conveniently prepared by means within the skill in the art such as described by Selva et al. , Synthesis, 1991, 1003-1004 wherein haloalkylarylenes are reacted with formaldehyde in acid (for example sulfuric or hydrochloric) in the presence of a quaternary ammonium phase transfer catalyst. Chloromethylation can also be performed using zinc chloride and parafor aldehyde in accordance with the method described by Daren in U.S. Patent 4,967,026. Alternatively, chloromethyl ethers are used to chloromethylate a haloalkyl arylene by methods similar to that taught by Raley in U.S. Patent 3,311,602, by Shinka, et al. J. Poly. Sci . Polym. Lett. Ed. 14(1) , l- 3 (1976) , and by Shigeo, et al. Chem. Abstr. 72:32290 (1970) , or by other means within the skill in the art. In another aspect, hydrohalogenating agents such as HBr are added to alkenyl arylenes such as styrene under radical forming conditions such as taught by Martan in U.S. Patent 4,228,106 or Plesmid in U.S. Patent 3,321,536 which patents are incorporated herein by reference in their entireties. In an extension of these works, vinylbenzyl chloride is hydrobrominated by this method. The sulfonation and thiolation steps are as described for the previous process. In addition to the methods disclosed above, a variety of other methods are also available for preparing the haloalkyl-functionalized polystyrene resins which are precursors to the mercaptosulfonic acid polymer catalysts. Representative approaches for preparing the haloalkylated polystyrene resins include (but are not limited to) those described or discussed by: a) P. C. Reeves and M. S. Chiles, "Phase Transfer Catalysts Anchored to Polystyrene," Tetrahedron e^t.srs (1979) , pages 3367-3370 b) M. Tomoi, et. al., "Novel Synthesis of Spacer-Modified Polymer Supports and Activity of Phase-Transfer Catalysts Derived from the Polymer Supports, " J. Polymer. Sci. Polymer Chem. Ed.. vol. 20 (1982) , pages 3015-3019 c) M. J. Farrall and J. M. J. Frechet, "Bromination and Lithiation: Two Important Steps in the Functionalization of Polystyrene Resins," J. Org. Chem. , vol. 41 (1976) , pages 3877-3882 d) S. P. McManus and R. D. Olinger, "Reactions of Cyclic Halonium Ions and Alkylene Dihalides with Polystyryllithium. Preparation of Haloalkylated Polystyrene," J. Org. Chem., vol. 45 (1980) , pages 2717- 2719 e) M. Haratake, et. al. "Sorption of Phenols on Anion-Exchange Resins Having .omega. -Oxoalkyl or .omega. - Hydroxyalkyl Spacer," Analytical Sciences, vol. 4 (1988) , pages 591-594 f) M. Gauthier and A. Eisenberg, "Alkylated Styrene lonomers with Variable Length Spacers . I. Synthesis," J. Polymer Sci. : Part A: Polymer Chem.. vol. 28 (1990), pages 1549-1568 g) P. Tundo, "Easy and Economical Synthesis of Widely Porous Resins; Very Efficient Supports for Immobilized Phase-Transfer Catalysts," Synthesis (1978), pages 315-316 h) Tachikawa, et. al. "Process for the Production of Silanes" (U. S. Patent 4,725,420) i) G. Zheng, et. al. "Synthesis of Bromoalkylated Crosslinked Polystyrene, " Xinan Shifan Haxiifi Xuehao. Ziran Kexueban. vol. 2 (1986) pages 68-70 j) M. L. Hallensleben, "Preparation of Poly(p- ( .omega. - lithiumalkyl) styrenes) and Their Use as Polymer Metalating Agents," Angew. Makromnl . Cham. , vol. 31 (1973) , pages 147-159 k) F. Dόscher, et. al., "Synthesis of Sulfoalkylated Styrene-Divinylbenzene Copolymers, " Ma romol. Chem.. Rapid Commun.. vol. 1 (1980) , pages 297- 302. It is to be understood that a haloalkylated polystyrene resin prepared in a manner such as that described in the above references could be further functionalized by the sulfonation and thiolation procedures previously described to provide a mercaptosulfonic acid polymer catalyst. Other representative references on methods for polymer modification or for uses of functional polymers include Akelah et al. , "Application of Functionalized Polymers in Organic Synthesis," Chem. Rev.. vol. 81 (1981) , pages 557-587; Frechet et al. , "Functionalization of Crosslinked Polystyrene Resins by Chemical Modification: A Review, " in "Chemistry and Properties of Crosslinked Polymers," S. Labana, ed., Academic Press, New York (1977) , pages 59-83; and Marechal, "Chemical Modification of Synthetic Polymers, " in "Comprehensive Polymer Science," vol. 6, Allen, ed. , Pergamon Press, New York, pages 1-47. Catalysts derived from polystyrenes will advantageously contain from 0.2 to 5 meq of mercapto/sulfonic acid functionality per g, most preferably from 2 to 4 meq/g. It will be understood that polymers, containing large amounts of mercapto/sulfonic acid functionality on a given carrier, pendant from a hydrocarbon chain, can be prepared by grafting vinylsulfonic acid, propenesultone, or the like, to the pendant carrier function, and converting the grafted polymer to materials having mercapto/sulfonic acid functionality. Catalytically-active polymers in which - is an ionic bond can advantageously be prepared from ion-exchange resins and reactive compounds, containing both mercapto and sulfonic acid functions. For example a strongly basic ion-exchange resin such as poly(vinylbenzyl amine) can be reacted with a compound such as 4-mercapto-l, 2-butanedisulfonic acid to produce catalytically-active material as represented by the equation: HSCH 2 CH 2 CH(S0 3 H) CH 2 S0 3 H 0 3 SCH 2 CH (SO3H) CH 2 CH 2 SH Representative strongly basic ion-exchange resins include Dowex™ 1X2-400, Amberlyst™ A-21, Dowex™ WGR-1, Dowex™ WGR-2 and Dowex™ MSA-1. The WGR resins are polypropyleneimines, conveniently obtained by condensation of epichlorohydrin with ammonia. Catalytically-active materials can also advantageously be prepared from an acidic ion-exchange resin, for example sulfonated polystyrene by reaction with an aminomercaptosulfonic acid, for example 2-mercapto-4- aminobenzene sulfonic acid, as represented by the equation: SH Representative strongly acidic cation-exchange resins include Dowex™ 50X2-400, Amberlyst™ A-21 and Dowex™ MSC- 1. In addition to the use of polymers from ethylenically unsaturated monomers, including copolymers, as insoluble supports for the catalytically-active species, the catalytically-active species can be attached to an inorganic support, for example a mineral, such as silica, alumina, aluminosilicates or glass, through the linking group -L- . A representative case is that wherein the linking group is -OSiO- or -0-P(=0) -0-, I O most preferably, -OSiO- . Catalytically-active species of Formula III will conveniently be incorporated in the backbone of condensation polymers, for example polyesters, polyamides, polycarbonates, polyurethanes, polysiloxanes, polyamines, polyethers, polyketones, polysulfones, polysulfoxides and the like. The divalent linking group, -L'-, can be selected from such structures as polyoxy(alk-di-yl) , polyoxy(ar-di-yl) , dioxy(alkar-di-yl) , polyoxy(aralk-di- yl) , polythio(alk-di-yl) , polythio(aralk-di-yl) , polythio- (ar-di-yl) , polythio(alkar-di-yl) , polythio(aralk-di-yl) , polyamido(alk-di-yl) , polyamido(ar-di-yl) , polyamido- (aralk-di-yl), polycarbonyloxy(alk-di-yl) , polycarbonyloxy(ar-di-yl) , polycarbonyloxy(alkar-di-yl) , polycarbonyloxy(aralk-di-yl) , polycarbonyldioxy(alk-di- yl) , polycarbonyldioxy(ar-di-yl) , polycarbonyldioxy(alkar- di-yl) , polycarbonyldioxy(aralk-di-yl) , polyamino(alk-di- yl) , polyamino(ar-di-yl) , polyamino(alkar-di-yl) , polyamino(aralk-di-yl) , polycyclimido(ar-di-yl) , polycycl- imido(alkar-di-yl) , polycyclimido(aralk-di-yl) , poly- carbonyl (alk-di-yl) , polycarbonyl(ar-di-yl) , polycarbonyl- (alkar-di-yl) , polycarbonyl(aralk-di-yl) , polyimido(alk- di-yl) , polyimido(ar-di-yl) , polyimido(alkar-di-yl) , polyimido(aralk-di-yl) , polyureylene(alk-di-yl) , poly- ureylene(ar-di-yl) , polyureylene(aralk-di-yl) , polyureylene alkar-di-yl), polycarboxamideoxy(alk-di-yl) , polycarboxamideoxy(ar-di-yl) , polycarboxamideoxy(alkar-di- yl) , polycarboxamideoxy(alkar-di-yl) , polycarbox¬ amideoxy(aralk-di-yl) , ar-di-yl, alkaryl-di-yl, aralkyl- di-yl and alkenoic-di-yl. Preferred divalent linking groups, -L'-, include di (carbonyloxy) hydrocarbylene, siloxy, dicarboxamidohydrocarbylene, di (oxycarbonyl) hydrocarbylene, dithiohydrocarbylene, and hydrocarbylene groups containing aromatic rings. During batch processing, the mercaptosulfonic acid catalyst is suitably present in an amount sufficient to enable condensation of the phenol with the ketone/aldehyde in a reasonable time. Preferably, the amount of mercaptosulfonic acid ranges from 0.01 equivalents to 2.0 equivalents of catalyst per 1.00 equivalents of the ke¬ tone/aldehyde. More preferably, the amount of mercapto¬ sulfonic acid catalyst is from 0.02 to 1.0 equivalent of mercaptosulfonic acid per equivalents of aldehyde/ketone. Most preferably, the reaction mixture will contain from 0.03 to 1.0 equivalent of mercaptosulfonic acid per equivalents of aldehyde or ketone under batch processing. When ketone/aldehyde is added over the course of a reaction (for example a continuous reaction) the previously stated preferred amounts refer to total catalyst and reactants added rather than catalyst present in a reaction mixture at a given moment. Those skilled in the art recognize that when a reactant is added incrementally or continuously, there is often a large excess of catalyst. The ratio of catalyst to ketone/aldehyde in the reaction mixture is advantageously greater than one, conveniently on the order of 20 equivalents to 1 equivalent. Due to the high activity of the mercaptosulfonic acid catalysts, good reaction rates and high selectivity can be obtained at temperatures below the melting point of phenol. The phenol reactant can advantageously be kept in the liquid state by addition of solvents, e.g., water, methylene chloride, diphenylmethane, etc. Low temperature reactions are often particularly advantageous, because the product diphenolic compounds crystallize in the reaction mixture and because lower reaction temperatures favor higher selectivity toward 4,4-bisphenolic products. The reaction temperature will accordingly advantageously be selected in the range from 0°C to 100°C, preferably from 15°C to 60°C. Temperature ranges can be chosen by routine experimentation, depending upon the ketone/aldehyde and phenol feeds. When excess phenolic compound is used as solvent, the temperature for the condensation is advantageously selected so that the phenol is in the liquid state. In the case of high-melting phenols, for example those melting above 180°C, the use of an inert solvent is preferred. Diphenylmethane has been found to be particularly useful for this purpose. Other useable inert solvents include, but are not limited to, the xylenes, mesitylene, the durenes, fluorobenzene, toluene, cyclohexane, chlorobenzene, halogenated aliphatic hydrocarbons and alkylnaphthalenes having low melting points. If a solvent/diluent is used, the amount used conveniently ranges from 5 mL to 1 L per mole of ketone or aldehyde. Preferably, from 200 mL to 400 mL are used per mole of ketone or aldehyde. The addition of water, generally in an amount up to a maximum of 5 percent by weight of total feed, is considered highly desirable in processes for the preparation of bisphenol A, because water lowers the freezing point of phenol and addition of water permits the condensations to be run at lower temperatures than otherwise. Most preferably, the amount of added water is from 1 percent by weight to 5 percent by weight of total feed. The reaction can advantageously be carried out by stirring the ketone or aldehyde and mercaptosulfonic acid into molten phenol in such a way that the temperature in the reaction vessel will not rise above 150°C. The molar ratio of phenolic reactant to ketone or aldehyde is advantageously selected so that at least two moles of phenol will condense with the ketone to produce a corresponding bisphenol or higher condensate. Therefore, molar ratios of 2:1 or higher will advantageously be selected. It is preferred to carry out the reactions using larger excesses of phenolic reactant, up to as much as 50 moles of phenol per mole of ketone or aldehyde. It will be understood that the excess phenol acts as a solvent or diluent, as well as a reactant. Lower ratios of phenol to ketone/aldehyde are generally accompanied by an increase in the amount of by¬ products formed. In the preparation of polyphenols, it has been found that molar ratios from 2:1 to 30:1 of phenol to aldehyde/ketone are preferred. More preferably, the reaction mixtures will contain from 4:1 to 25:1 molar ratios of phenol to aldehyde/ketone. Most preferably, the molar ratio is from 6:1 to 25:1 Since the condensation reaction is exothermic, the reactants, instead of being mixed together all at once, are optionally progressively mixed together at a speed depending upon the intensity of the cooling employed to maintain the temperature of the reaction medium within the optimum limits. After the mixing of the reactants, they are preferably left in contact for some time in order to complete the condensation. The duration of the introduction of the reactants during a batch process conveniently varies from 15 min to 1 h. In batch processes, the reactants and the catalyst are preferably thoroughly stirred mechanically to assure better mixing, and hence an improved space-time yield. When the process of this invention is conducted batchwise, the reaction time is advantageously in the range of 0.1 to 20 hours depending on the reaction conditions including the amount of the catalyst used, the reaction temperature, and specific reactants, solvents and products. The process of this invention can also be run in continuous mode, more preferably by use of a series of continuous stirred tank reactors, the use of which approximates plug flow reaction conditions. It is preferred to carry out the process of this invention under continuous reaction conditions. The pressure in the reaction zone is not critical, but preferably ranges from 0.001 to 10 bar (0.1 to 1000 kPa) , and more particularly from 0.5 to 3 bar (50 to 300 kPa) . In many cases, it will be preferred to carry out the reactions under ambient pressure, that is, 1 bar (100 kPa) . During the reaction, one mole of water is evolved for each mole of ketone/aldehyde undergoing the condensation with phenol. It has been found that adding water to the reaction mixtures can be advantageous for decreasing the melting point of phenol. The water evolved during the reactions need not be removed by distillation/entrainment with an inert solvent in order to attain high reaction rates. In some cases, however, it will be preferred to entrain and remove water from the reaction mixture, in order to increase reaction rates. It has been found that the soluble mercaptosulfonic acid catalysts can advantageously be removed from the crude product by extraction with water. The aqueous extracts can be concentrated and recovered mercaptosulfonic acid catalyst can be optionally recycled to subsequent runs. When the phenolic starting material is phenol, a solution of the mercaptosulfonic acid in phenol is conveniently recovered and is optionally recycled without further purification. The acid concentration can be reduced below about the limits of detection, and probably below 1 ppm by weight of acid, by repeated extractions with water. The facile removal of catalyst from the reaction mixtures is a significant advantage over the prior art, using mixtures of condensing agents. It is within the practice of this invention to remove the mercaptosulfonic acid by continuous countercurrent extraction. The time for phase separation during extraction of the acid catalyst is of the order of 10-15 min under batch conditions, without a drag layer. Stirring speed during the extraction in a mixer/settler is adjusted so as to avoid emulsion formation. The soluble mercaptosulfonic acid catalysts can also be removed from reaction mixtures by extraction with a solution of an alkali metal hydroxide, carbonate or bicarbonate. In addition, the soluble mercaptosulfonic acid catalysts can be removed from reaction mixtures by passing the reaction mixture through a column of anion-exchange resin or amine resin, such as Dowex™ WGR. A water purge from the process will contain phenol plus catalyst. This purge is advantageously treated to remove phenol by extraction with methyl isobutyl ketone before being sent to a bio-pond for disposal. For isolation of BHPF from reaction mixtures, made using a soluble catalyst, a phenol/water mixture is preferably distilled from the water-washed mixture until the weight ratio of phenol:BHPF is below 1.5:1. Most preferably, phenol is removed until the phenol:BHPF weight ratio is from 1.5:1 to 0.5:1. It has been found particularly advantageous to dissolve the resulting material in hot methylene chloride and cool the resulting solution to obtain crystalline BHPF. Very highly purified BHPF accordingly can be obtained by a process wherein a resulting crude product is washed with water to remove (HS) a -θ- (S0 3 H) b ; the resulting acid- free mixture is distilled to remove phenol and water until the phenol:9, 9-bis- (4-hydroxyphenyl) fluorene weight ratio is less than 1.5; the resulting mixture is taken up in hot methylene chloride and the resulting solution is cooled to produce crystalline 9, 9-bis- (4-hydroxyphenyl) fluorene. BHPF purified in this way can be used to make ultrahigh quality polycarbonate resins. Excess phenol can also be removed by boiling the reaction mixture repeatedly with water, optionally with the use of a water-miscible organic solvent such as methanol. The aqueous solution is separated each time and the product, then practically pure, is dried. Another effective method of removing excess phenol is by steam distillation. The reaction product solution is optionally then concentrated by evaporation and repeatedly extracted with boiling water for the removal of excess phenol. The product so obtained is optionally then recrystallized for further purification. BHPF can be isolated from the reaction mixtures in several additional ways. The method selected will depend on the degree of purification desired as well as the composition of the reaction mixture, the desired production rate, etc. When extensive purification is undesirable or inappropriate, the mixture, after being treated to remove catalyst, can be treated with a volume of hot water sufficient to dilute the mixture and bring about precipitation of BHPF. Alternatively, the reaction mixture can be added to hot water and the phenol removed in the form of a water/phenol azeotrope until the phenol content is lowered sufficiently to permit precipitation of BHPF from the mixture. The BHPF solids can be collected and dried before use or can be used in the form of a slurry. When more extensive purification of BHPF is desired, the solids can be purified by precipitation from a solvent, for example diphenylmethane or methylene chloride. Another method for isolating BHPF comprises adding to the reaction mixture, at the end of the reaction, a solvent, boiling at a higher temperature than phenol, and removing phenol from the phenol/BHPF/solvent mixture until BHPF crystallizes or precipitates from the mixture. This method can be carried out by adding diphenylmethane or triisopropylbenzene to a reaction mixture, from which catalyst has been extracted or removed, prior to distilling the mixture. Alternatively, the solvents can be added to the initial reaction mixture so that the reactions are run in the presence of the solvent. The reaction mixture is worked up by extracting to remove catalyst and by then distilling to remove solvent and phenol, until BHPF crystallization occurs. BHPF can also be isolated by adding to a reaction mixture a solvent, which boils at a higher temperature than phenol and dissolves sufficient BHPF, in the absence of phenol, that removing phenol from the phenol/BHPF/solvent mixture provides a homogeneous solution, cooling of which causes crystallization of BHPF. Solvents meeting these requirements include diphenylmethane, diphenyl ether, dodecane, naphthalene, Isopar™ (hydrocarbon mixture commercially available from Exxon Corporation) and triisopropylbenzene. Further purification can also be accomplished, after removing catalyst from the reaction mixture, by distilling to remove phenol to a level at which BHPF crystallizes from the phenol/BHPF mixture. The BHPF solids obtained can be isolated by conventional means and then further treated, e.g., by washing with water to remove phenol. An alternative method for obtaining high purity BHPF comprises removing catalyst from the reaction mixture, distilling phenol from the reaction mixture to a phenol/BHPF level such that dilution of the distillation residue with a solvent induces, crystallization of the BHPF from the phenol/BHPF/solvent mixture. For example, phenol can be removed by distillation until the distillation residue contains 50 percent by weight of phenol and 50 percent by weight of BHPF. Methylene chloride, triisopropylbenzene or toluene can be added to the residue and the resulting solution can be cooled to bring about crystallization of highly purified BHPF. Another procedure for isolating pure BHPF solid from the reaction comprises removing the mercaptosulfonic acid catalyst, distilling phenol from the resulting mixture, to produce a still residue, to which addition of a solvent induces crystallization of BHPF. For example, a still residue containing 80 percent by weight of phenol and 20 percent by weight of BHPF can be diluted with a solvent, for example dichloromethane or toluene, to induce crystallization of BHPF. In addition, BHPF can be isolated from a reaction mixture, by removing the mercaptosulfonic acid catalyst, adding to the resulting reaction mixture a solvent, which forms an azeotrope with phenol and in which BHPF is soluble in the absence of phenol, and removing phenol from the mixture by azeotropic distillation. Cyclohexanol is exemplary of a solvent, which will form an azeotrope with phenol and from which BHPF will precipitate upon cooling the still residue from the azeotropic distillation. Similarly, phenol can be removed from the reaction mixtures by addition of a solvent, which forms an azeotrope with phenol. After removing phenol by azeotropic distillation, the still residue is cooled and BHPF crystallizes out from the cooled mixture. In any of the purification processes which result in a crystalline product, the catalyst is optionally not removed before crystallization of product but rather either tolerated in the product or removed from the crystals, for instance by washing or other means within the skill in the art, after crystallization. In some cases, the condensation of phenol with ketones or aldehydes can be run in a solvent, e.g., methylene chloride, from which the product will precipitate during the course of the reaction, as is described in more detail for the preparation of bisphenol A. A representative solvent used for crystallization of BHPF, methylene chloride, can be recovered from the mother liquors by batch distillation and recycled back to the process. The still bottoms contain BHPF and methylene chloride and can be cooled to recover additional BHPF. BHPF crystals thus formed are conveniently recovered using a basket centrifuge or pressure filter and can be recycled back to a main crystallizer. Crude mother liquor can also be recycled back to the phenol evaporation section. When methylene chloride is used as solvent for crystallizing BHPF, a common vent header for collecting all vents from storage tanks and safety relief systems is recommended. The vent header system advantageously includes a flow measurement device in the inlet to a carbon adsorption unit and a VOC (volatile organic compound) analyzer for the exit gas. The exit gas should contain less than 100 ppm of methylene chloride. A complete effluent treating system will advantageously include means for removing organics from process waters and means for removal of particulates from vent gas, e.g a water venturi to scrub particulates from the vent header. A further advantage of the catalysts used in the practice of this invention is that the catalysts can be used to isomerize the crude product mixture, which typically contains (4-hydroxyphenyl) (2-hydroxyphenyl) compounds, the major bis- (4-hydroxyphenyl) compounds, and condensates, to produce more of the bis- ( -hydroxyphenyl) compounds. The mercaptosulfonic acid .catalysts of this invention are considerably less corrosive to stainless steel than the mixed catalysts used heretofore. Corrosion rates for stainless steel, below 0.00254 cm/year, have been measured. The reaction mixtures are believed to be substantially free of halide ions, wherein "substantially free" means less than 5000 ppm of chloride ions. The process of this invention is advantageously carried out under conditions such that the concentration of chloride is below 5000 ppm, preferably below 1000 ppm, most preferably below 100 ppm. It is believed that the low corrosion rate is related to the absence of mineral acids, such as hydrochloric acid or sulfuric acid, from the reaction mixtures. The occurrence of corrosion in reactions using mineral acids has been noted by Knebel et al. '594 and Faler '995, supra. The insoluble catalysts of this invention can be filtered from the reaction mixtures, washed with a mixture of ketone/aldehyde and phenol, and recycled to subsequent runs. Alternatively, the insoluble catalysts are used in fixed beds and the condensations of phenols with aldehyde/ketone is done in continuous upflow, crossflow or downflow fashion. When fixed bed catalytic reactors are used, the catalytically-active resins remain in the resin beds and need not be removed. Further embodiments of this invention will be determined by the reactants used, the catalyst selected, the diluent, if any, and the reactor employed. For example, when using a soluble catalyst for the condensation of phenol with 9-fluorenone, without a diluent, other than excess phenol or in the presence of a diluent which does not cause precipitation of product, it will generally be preferred to use a high ratio of phenol to fluorenone to maximize selectivity to the desired bisphenol product. A particularly preferred process is one wherein the molar ratio of phenol :fluorenone is from 4:1 to 25:1; the reaction temperature is from 25°C to 50°C; the catalyst is ercaptopropanesulfonic acid or mercaptobutanesulfonic acid, used in an amount from 5 to 10 molar percent with respect to fluorenone; the process is carried out under ambient pressure or under vacuum to remove water of reaction and increase the reaction rate; no cosolvent is used; the catalyst is removed from the product by extraction with water using a wash column or by batch extraction; the water extracts thus obtained are concen¬ trated and recycled to the process; the product is isolated by removing excess phenol to a weight ratio from 1.5:1 to 0.5:1 of phenol:BHPF and the product is precipitated with dichloromethane. When an insoluble catalyst is used, a particularly preferred process is one wherein the molar ratio of phe¬ nol:fluorenone is from 4:1 to 25:1; the condensation is carried out at a temperature from 40°C to 60°C; no cosolvent is used; the catalyst is PMBSA (polymer- supported mercapto butane sulfonic acid) ; the condensation is carried out in a continuous plug flow reactor; the reaction is carried out at ambient pressure or under reduced pressure to remove water of reaction and increase the reaction rate; the product is isolated by removing excess phenol to a weight ration from 1.5:1 to 0.5:1 of phenol:BHPF and the product is precipitated with dichloromethan . The process for making BHPF can also be carried out at molar ratios of phenol:fluorenone from 7:1 to 5:1 in the presence of 0.05 to 0.15 equivalent of MPSA or MBSA per mole of fluorenone, wherein methylene chloride is added to the reaction mixture after conversion of at least 20 percent of fluorenone has occurred; heating the resulting mixture under reduced pressure to remove an azeotrope of methylene chloride and water; and cooling the mixture at the end of the condensation reaction to cause precipitation of BHPF. The condensation of phenol with fluorenone can further be carried out using a feed containing from 5:1 to 3:1 molar ratio of phenol:fluorenone and from 0.05 to 0.15 equivalent of MPSA or MBSA per mole of fluorenone, diluted with from 10 percent by weight to 30 percent by weight of methylene chloride. Crystalline BHPF can be collected from the cooled reaction mixture. In addition, BHPF can be prepared from a reaction mixture, containing from 18:1 to 12:1 molar ratios of phenol:fluorenone and 0.025-0.075 equivalent of MPSA or MBSA per mole of fluorenone at a temperature from 50°C to 80°C, wherein the mixture at the end of the reaction is diluted with 10-20 volumes of water to extract mercaptosulfonic acid catalyst, the thus-washed mixture is distilled to a phenol:BHPF weight ratio from 1.5:1 to 1:1 and cooled to bring crystallization of BHPF. The crystalline BHPF is removed by filtration and washed with methylene chloride and then with water. A process in which the product is precipitated in the reaction mixture is preferred for the preparation of bisphenol A, more particularly a process wherein the phenol:acetone feed contains from 6:1 to 15:1 molar ratios of phenol:acetone; the condensation is carried out at a temperature from 25°C to 35°C; the reaction mixture contains up to 5 percent by weight of water to lower the freezing point of phenol; the catalyst is 3- mercaptopropanesulfonic or 4-mercaptobutanesulfonic acid in an amount from 0.05 to 0.50 equivalent per mole of acetone in the acetone:phenol feed; the reaction is carried out under ambient pressure; and the crystalline bisphenol A produced by the process is removed by filtra¬ tion or centrifugation. Further processing can include washing the bisphenol A with water to partially remove soluble catalyst, and removing additional soluble catalyst by treatment with an anion exchange resin. It is believed that a preferred reactor configuration for this process is a series of continuous stirred tank reactors, so as to approximate plug flow reaction conditions. Other process variations, include, but are not limited to: (a) preparation of bisphenol A in neat phenol, using a soluble catalyst, with precipitation of bisphenol A in the reaction mixture and (b) preparation of bisphenol A in phenol with a complex-forming cosolvent and soluble catalyst, with precipitation of bisphenol A in the reaction mixture. More particularly, it is preferred to select a catalyst wherein at least 99 percent of the bisphenol A that crystallizes during the reaction is ,4-bisphenol A. Such catalysts include soluble mercaptosulfonic acids in which a and b are each independently integers from 1 to 4. Preferred conditions include reaction temperatures from 0° C to 50°C, more preferably from 20°C to 40°C. Representative complex-forming solvents for bisphenol A include diethyl ether, acetone, ethanol, propanol, dioxane, acetic acid, acetonitrile, methylene chloride or carbon tetrachloride . The complex-forming solvents complex preferentially with the 4 ,4-diphenolic isomer so that the resulting complex has solubility properties, differing from that of the unco plexed 2, 4-diphenolic compound and can be readily separated therefrom. These processes can be run under varying pressure and temperature conditions, as well as reactant, cosolvent and catalyst concentrations, as can be determined by routine experimentation. In one aspect, a most preferred process of this invention is that wherein the ketone is 9-fluorenone, the phenol is unsubstituted and the product is 9,9-bis-(4- hydroxyphenyl) fluorene; the molar ratio of phenol to fluorenone is from 8:1 to 25:1; the reaction mixture contains from 0.05 to 0.20 equivalent of mercaptosulfonic acid per mole of fluorene,- the mercaptosulfonic acid compound is 3-mercaptopropanesulfonic acid or 4-mercapto- butanesulfonic acid and the process is carried out at a temperature from 45°C to 60°C. An equally preferred process is that wherein the ketone is acetone, the phenol is unsubstituted and the product is 2,2-bis- (4-hydroxyphenyl)propane; the molar ratio of phenol to acetone is from 6:1 to 15:1; the reaction mixture contains from 0.10 to 0.50 equivalent of mercaptosulfonic acid per mole of acetone; the mercapto¬ sulfonic acid compound is 3-mercaptopropanesulfonic acid or 4-mercaptobutanesulfonic acid and the process is carried out at a temperature from 15°C to 60°C. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to the fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following examples, the temperatures are set forth uncorrected in degrees Celsius. Unless otherwise indicated, all parts and percentages are by weight. REACTORS Reactor design 1: A 500-mL reactor prepared from PFA Teflon™ is fitted with a thermocouple port, water condenser topped with nitrogen inlet, mechanical stirrer, drain port, and sampling port. Heating is provided with an infrared heat lamp and the temperature is controlled with an electronic thermometer/temperature controller. Reactor design 2: A capped 4 dram glass vial with a magnetic stirrer. Heating is regulated by placing the vial in a temperature-controlled aluminum block heater. Reactor design 3: A 100-mL jacketed glass reactor is fitted with a thermometer port, magnetic stirrer, nitrogen inlet, and sampling port. Heating is provided and the temperature is controlled by circulating glycol solution of the appropriate temperature through the jacketed flask using a Neslab Model RTE-220 circulating bath. Reactor design 4: A 1.5 L, 2 L, or 3 L jacketed glass reactor fitted with a thermometer/sampling port, nitrogen inlet, and mechanical stirrer. Heating is provided and the temperature is controlled by circulating glycol solution of the appropriate temperature through the jacketed flask using a Neslab Model RTE-220 circulating bath. ANALYTICAL Analytical method 1: A Varian HPLC system (Model 9010 solvent delivery system, Model 9095 Autosampler, Model 9065 Polychrom diode array detector) interfaced with a Varian Star workstation is used for analysis. Area percent analysis is reported at 282 nm. Percent conversion is determined by an external standard method using calibrated concentration curves for each major component. Analytical HPLC samples are prepared by careful quantitative dilution of reaction samples (range: 400-500 times dilution) . Column: Waters Nova-Pak™ C-18 (60 Angstrom, 4 micron, 3.9 X 150 mm) . Chromatography conditions: flow rate 1.0 L/min, solvent gradient (solvent A = water, solvent B = acetonitrile) 0 min: 65 percent A/35 percent B, 9 min: 60 percent A/40 percent B, 18 min: 55 percent A/45 percent B, 24 min: 45 percent A/ 55 percent B, 48 min: 5 percent A/ 95 percent B, 52 min: method end (10 min equilibration before and after runs) . Analytical method 2: A Hewlett-Packard HPLC system (Model 1084B solvent delivery system, Model 79850B LC terminal) is used for analysis. Area percent analysis is reported at 254 nm. Percent conversion is determined by an external standard method using calibrated concentration curves for each major component. Analytical HPLC samples are prepared by careful quantitative dilution of reaction samples (range: 400-500 times dilution) . Column: Waters Nova-Pak™ C-18 (60 Angstrom, 4 micron, 3.9 X 150 mm) . Chromatography conditions: flow rate 1.0 mL/min, solvent gradient (solvent A = water, solvent B = acetonitrile) 0 min: 65 percent A/35 percent B, 9 min: 60 percent A/40 percent B, 18 min: 55 percent A/45 percent B, 24 min: 45 percent A/ 55 percent B, 36 min: 25 percent A/ 75 percent B, 38 min: 65 percent A/35 percent B, 38 min: method end. NOTE: This method gives a smaller response (approximately one-half the area) for the 2,4-BHPF and the two:three adduct BHPF peaks relative to the 4,4-BHPF peak than either methods 1 or 3 using the diode array detector. Analytical method 3 : A Varian HPLC system (Model 9010 solvent delivery system, Model 9095 Autosampler, Model 9065 Polychrom diode array detector) interfaced with a Varian Star workstation is used for analysis. Area percent analysis is reported at 282 nm. Percent conversion is determined by an internal standard method using a solution of 0.0508 weight percent acetophenone in 60/40 (weight/weight percent) methanol/water for preparing the samples. Analytical HPLC samples are prepared by careful quantitative dilution of reaction samples. Column: Waters Nova-Pak™ C-18 (60 Angstrom, 4 micron, 3.9 X 150 mm) . Chromatography conditions: flow rate 1.0 mL/min, solvent gradient (solvent A = water, solvent B = methanol) 0 min: 55 percent A/45 percent B, 20 min: 15 percent A/85 percent B, 25 min: 10 percent A/90 percent B, 30 min: 55 percent A/ 45 percent B, 35 min: method end (10 min equilibration before and after runs) . Analytical method 4: The experimental setup of Method 1 is used. The chromatography conditions are: flow rate 1 mL/min, solvent gradient (solvent A = water, solvent B = methanol) 0 min: 55 percentA/45 percentB, 20 min: 15 percentA/85 percentB, 25 min 10 percentA/90 percentB. Analysis - Internal Standard method using 0.0508 percent acetophenone in 60 percent methanol/water. Average rel. std. deviations ranges from 1 to 2 percent, depending upon peak analyzed. Analytical method 5: The reaction mixture is diluted with acetonitrile to a concentration of 0.01-0.1 percent by weight of components and the diluted sample is analyzed by HPLC on a Waters NovaPak™ C18 column (10.16 cm x 0.635 cm inner diameter) connected to a Varian 9100 UV detector, set at 280 nm. The column temperature is 30°C, the pressure is 140 atm at 0 min, the absorption full scale for the detector is 2.0, the integrator attenuation is 3 and the chart speed is 0.5 cm/min. The autosampler injects 20 microliters of sample onto the column every 36 min. Reservoir A contains megapure water and reservoir B HPLC grade acetonitrile. The following protocol is used: Tjns Flow Rate %B (min) (mL/min) 0 1.0 40 8 1.0 40 20 1.0 60 26 1.0 99 30 1.0 40 * __ percent The peak area generated by each component in the sample is used with its known response factor, and the dilution ratio, to calculate the concentrations of each component in the sample solution. REAGENTS Fluorenone (Aldrich 98 percent), approximately 0.5 percent fluorene and methyl-fluorenes Acetone (Baker reagent, dried over molecular sieves) Diphenylmethane (Penta International, 99+ percent distilled grade) Phenol (Dow Chemical 99+ percent) , approximately 100 ppm H 2 0 + 100 ppm impurities Sodium 3-mercaptopropanesulfonate: Source A: 90 percent purity (Aldrich) Source B: 90 percent purity (Raschig Corp.) 3-Mercaptopropanesulfonic acid (MPSA) : Source A: Prepared from 90 percent Aldrich sodium 3-mercaptopropanesulfonate by reaction with HCl or treatment in an ion-exchange column Source B: Prepared from 90 percent Raschig Corp. sodium 3-mercaptopropanesulfonate Sodium 2-mercaptoethanesulfonate: 98 percent (Aldrich) 4-Mercaptobutanesulfonic acid (MBSA) : prepared from 1,4-butanesultone (Aldrich) by reaction with NaSH, Ba(SH) 2 or an alkali metal thioacetate in accordance with R. Fischer, supra, A. Mustafa, supra, or Chem. Abs.. 90:86742m (1979) . 2-Benzyl-4-mercaptobutanesulfonic acid: prepared from 1,4-butanesultone (Aldrich) and benzyl bromide in accordance with M. B. Smith et al. , "Lithium Aluminum Hydride-Aluminum Hydride Reduction of Sultones," . Org. Chem. f vol. 46 (1981), pages 101-106 or T. Durst et al. , "Metallation of 5- and 6-membered ring sultones, " Can. J. Chem.. vol. 47 (1969), pages 1230-1233. 2,3-Dimercaptopropanesulfonic acid: prepared from sodium 2,3-dimercaptopropanesulfonate (Aldrich, 95 percent) by neutralization with HCl or treatment with an acid ion-exchange resin, for example DOWEX™ MSC-1. 2,2-Bis(mercaptomethyl) -1,3-propanedisulfonic acid: prepared from 2,2-bis(bromomethyl) -1,3-propanediol (Aldrich, 98 percent) as follows: A mixture of 2,2-bis- (bromomethyl) -1,3- propanedisulfonic acid (200.0 g, 0.764 mole, 1.00 equivalent) and sodium sulfite (211.7 g, 1.68 mole, 2.20 equivalents) in 500 mL of deionized water is allowed to react under reflux (108°C) for 28 h. At this time, additional sodium sulfite (105.9 g, 0.840 mole, 1.10 equivalent) is added and the mixture is allowed to react for 3 additional days under reflux. At this point, the mixture consists of a clear solution and a considerable amount of solids. The mixture is cooled to room temperature and saturated with gaseous hydrogen chloride. An exotherm to 43°C is observed. The mixture becomes homogenous and yellow in color during the early stages of HCl addition. As the mixture becomes saturated with HCl, a voluminous white precipitate is formed. The solution is cooled to room temperature and filtered to remove solid salts, which are primarily sodium chloride and sodium bromide. Water is removed from the filtrate to provide 2,2-bis- (hydroxymethyl) -1, 3-propanedisulfonic acid (190.7 g) as a highly viscous amber oil (glass) . Alternatively, the reaction mixture can be worked up by dilution with 200 mL of ethanol or methanol, after which the solid is removed by filtration. Solvent is removed from the filtrate on a rotary evaporator, to produce a white solid containing mainly disodium 2,2-bis- (hydroxymethyl) -1, 3-propanedisulfonate. Concentrated hydrochloric acid can be added to the solid product to give the soluble disulfonic acid, plus insoluble sodium chloride and sodium bromide. p-Xylene (400 mL) is added to the 2,2-bis- (hydroxymethyl) -1,3-propanedisulfonic acid and the resulting two-phase mixture is heated under reflux (135- 150°C pot temperature) to remove water, produced by the dehydration, in the form of an azeotrope in a Dean-Stark trap. After 8 hours' heating under reflux, the mixture is allowed to cool to room temperature and the upper xylene phase is decanted from the lower viscous product phase. Water (300 mL) is added to the cooled, lower phase containing 2, 2-bis- (hydroxymethyl) -1, 3-propanedisulfonic acid bis-sultone to produce a large mass of white solid. The white solid (bis-sultone) is removed by filtration, slurry washed extensively with water and with methanol and dried in a vacuum oven To a solution of sodium bicarbonate (9.6 g, 114 mmol, 2.6 equivalents) in 30 mL of water is slowly added thiolacetic acid (7.5 g, 96 mmol, 2.2 equivalents) . The resulting solution of sodium thiolacetate is added to a solution of 2,2-bis- (hydroxymethyl) -1, 3-propanedisulfonic acid bis-sultone (10 g, 43.8 mmol, 1.00 equivalent) in 280 g of acetonitrile. After all the thiolacetate is added, the resulting mixture is allowed to stand overnight at ambient temperature. Solvent is removed using a rotary evaporator to give 19.6 g of ring-opened bis- (thioacetate) adduct as a tan, flaky solid. The thioacetate adduct (18.2 g) is hydrolyzed by stirring overnight at ambient temperature in a nitrogen- saturated mixture of 10 percent sodium hydroxide (20 g) and 100 g of water. The mixture is acidified to pH 3 with 10 percent aqueous hydrochloric acid solution. Solvent is removed from the resulting mixture in a fume hood, using a rotary evaporator. The residue is dissolved in 50 mL of water and saturated with hydrogen chloride gas. The resulting solid salt is removed by filtration and the filtrate is concentrated using a rotary evaporator to give 2,2-bis- (mercaptomethyl) -1, 3-propane-disulfonic acid as a viscous dark-colored oil. Alternatively, the thioacetate adduct can be hydrolyzed by stirring with concentrated hydrochloric acid, removing the solid salt product by filtration and removing water from the filtrate using a rotary evaporator. ABBREVIATIONS nm = nanometers uv = ultraviolet rpm = revolutions per minute mmol = millimoles HPLC = high pressure liquid chromatography BHPF = 9, 9-bis- (4-hydroxyphenyl) fluorene = 4,4-isomer = BF (also designated herein as 4, 4-BHPF) MPSA = 3-mercaptopropanesulfonic acid MBSA = 4-mercaptobutanesulfonic acid FN = Fn = 9-fluorenone 2,4-isomer = 9- (2-hydroxyphenyl) -9- (4- hydroxyphenyl) fluorene DPM = diphenylmethane BPA = 2,2-bis- (4-hydroxyphenyl)propane = bisphenol A n/d = not determined EXAMPLE 1 ΓONΠENSATTON OF 9-FLUORENONE WTTH PHENOL: .3-MERCAPTO- PROPANESTTT.FONIC ACID) 9-Fluorenone (20.0 g, 0.111 mole, 1.0 equivalents) and molten phenol (156.7 g, 1.66 mole, 15.0 equivalents) were added to a 500 mL PFA Teflon™ reactor (reactor design 1) . The reaction mixture was heated to 65°C with stirring at 300-350 rpm under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.864 g, 5.53 mmol, 0.0498 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 65°C. The mixture turned dark yellow-orange upon adding the catalyst and gradually faded to a lighter yellow color as the reaction progressed. A slight exotherm to 66°C was observed. The exotherm persisted for 10 minutes before the mixture cooled to the reaction temperature of 65°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC (Analytical method 1) . The 9-fluorenone was found to be completely consumed within 120 minutes with a product composition, determined by quantitative HPLC, of 98 percent of 9,9-bis-(4- hydroxyphenyl ) - fluorene . The product was further analyzed by a combinat ion of HPLC and UV ( 282 nm) and contains : percent by area product 96 . 9 9 , 9-bis- (4 -hydroxyphenyl ) fluorene (BHPF) 2 .4 9 - ( 2 - hydroxyphenyl ) - 9 - ( 4 - hydroxyphenyl ) - fluorene (2 , 4- isomer) 0 .7 adduct containing two fluorene units and three phenolic units (two : three adduct) EXAMPLE 2 GENERATION OF -MERCAPTOALKANESULFONIC ACTDS FROM THETR SODTUM SALTS IN THE REACTION MIXTURE A. The procedure of Example 1 was repeated except that the catalyst was prepared in situ from 90 percent sodium 3-mercaptopropanesulfonate (0.854 g, 4.79 mmol, 0.0431 equivalents) and 95-98 percent sulfuric acid (0.48 g, 4.9 mmol, 0.044 equivalents) and the reaction was conducted at 85°C. The 9-fluorenone was completely consumed between 60 and 120 minutes, giving a final isomer distribution, determined as in Example 1, of: % by area product 95.3 4,4-isomer (BHPF) 3.6 2,4-isomer 1.1 two-three adduct % __ percent B. The procedure of Example 2A was repeated except that 98 percent sodium 2-mercaptoethanesulfonate (0.779 g, 4.75 mmol, 0.0427 equivalents) and 95-98 percent sulfuric acid (0.48 g, 4.9 mmol, 0.044 equivalents) were used as catalysts. The reaction was conducted at 85°C. The 9-fluorenone was completely consumed within 60 minutes, giving a product isomer distribution, as described in Example 2A, of: % by area product 91.7 4, 4-isomer 6.6 2,4-isomer 1 . 7 two : three adduct % = percent These experiments demonstrate that 2-mercaptoethane- sulfonic acid, generated in the reaction mixture, is an effective condensing agent for the process. EXAMPLE 3 CONnENSATTON USING SULFURTC ACTD AND -MERCAPTOPROPinNTC ACTT. (COMPARATIVE EXAMPLE) 9-Fluorenone (20.0 g, 0.111 mole, 1.0 equivalents) and molten phenol (156.7 g, 1.66 mole, 15.0 equivalents) were added to the reactor (reactor design 1) . The reaction mixture was heated to 65°C with stirring a pad of nitrogen. 3-Mercaptopropionic acid (0.588 g, 5.54 mmol, 0.0499 equivalents) was added to the reaction mixture at 65°C, followed by the slow addition (over 1 minute) of concentrated (95-98 percent) sulfuric acid (0.551 g, 5.62 mmol, 0.0506 equivalents) to the reaction mixture at 65°C. The mixture turned purplish-orange upon addition of the sulfuric acid and gradually faded to a yellow-orange color within 5-10 minutes. A slight exotherm to 66-67°C, was observed. The exotherm persisted for 15 minutes before the reaction mixture cooled to the reaction temperature of 65° C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be completely consumed between 240 and 420 minutes. HPLC analysis (analytical method 3) gave a product distribution: % by area product 93.0 9, 9-bis- (4-hydroxyphenyl) fluorene 5.5 2,4-isomer 1.5 two:three adduct % = percent This example shows that the prior art process is slower than the process of Examples 1 or 2 and that the resulting product contains less of the 4,4-isomer, than produced by the process of Examples 1 or 2. EXAMPLE 4 EFFECT OF ADDED WATER IN FLUORENONE PHENOLATTONS USING MPSA (PHENOL AS SOLVENT) A. 9-Fluorenone (138.1 g, 0.770 mole, 1.00 equivalents) and molten phenol (1500 g, 15.9 mole, 20.8 equivalents) was added to the reactor (reactor design 4, 2 L) . The reaction mixture was heated to 45°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (8.28 g, 53.0 mmol, 0.0692 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 22 percent consumed within 9 minutes, 52 percent consumed within 30 minutes, 76 percent consumed within 1 hour, 92 percent consumed within 1.75 hours, and 100 percent consumed within 3.5 hours. HPLC analysis (analytical method 3) gives the following relative area percent analysis for the reaction products at 100 percent conversion: % by area product 96.9 9, 9-bis (4-hydroxyphenyl) fluorene 2.4 2,4-isomer 0.6 two:three adduct % = percent B. 9-Fluorenone (6.44 g, 0.0358 mole, 1.00 equivalents), molten phenol (70.0 g, 0.744 mole, 20.8 equivalents), and deionized water (1.93 g, 0.107 mole, 3.00 equivalents) was added to the reactor (reactor design 3) . The reaction mixture was heated to 45°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.385 g, 2.47 mmol, 0.0690 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45° C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 4 percent consumed within 9 minutes, 13 percent consumed within 1 hour, 29 percent consumed within 3.5 hours, and 94 percent consumed within 20.5 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 94 percent conversion: j. by area product 96.5 BHPF (4,4-isomer) 2.9 2,4-isomer 0.6 two:three adduct % _- percent These experiments show that higher reaction rates and lower amounts of undesirable by-products are obtained, in the absence of additional water. EXAMPLE 5 CONDENSATION OF FLUORENONE WTTH PHENOL USING OTHER CONDENSING AGENTS -. 4-MERCAPTQBUTANESULFONIC ACID 9-Fluorenone (82.9 g, 0.460 mole, 1.00 equivalents) and molten phenol (900 g, 9.56 mole, 20.8 equivalents) was added to the reactor (reactor design 4, 2 L) . The reaction mixture was heated to 45 °C with stirring under a pad of nitrogen. 4-Mercaptobutanesulfonic acid (5.41 g, 31.8 mmol, 0.0692 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 17 percent consumed within 5.5 minutes, 58 percent consumed within 30 minutes, 83 percent consumed within 1 hour, 95 percent consumed within 1.75 hours, and 100 percent consumed within 3.5 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products at 100 percent conversion: ■ by area product 97.0 BHPF 2.5 2,4-isomer 0.5 two:three adduct % «= percent B_ ^ 2,2-BIS- (MERCAPTOMETHYL) -1, 3-PROPANEDISULFONIC ACID To a 4 dram vial (reactor design 2) was added a mixture of fluorenone (0.40 g, 2.22 mmol, 1.00 equivalents) and phenol (2.10 g, 22.3 mmol, 10.0 equivalents) The capped vial was placed into the heating control block regulated at 63°C and stirring was begun. 2, 2-Bis (mercaptomethyl) -1, 3-propanedisulfonic acid (0.029 g, 0.098 mmol, 0.044 equivalents) was added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 25 percent consumed in 1.5 hours. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 25 percent conversion: % by area product 95.7 BHPF 3.4 2,4-isomer 0.9 two:three adduct % = percent £ ^ 2,3-DIMERCAPTOPROPANESULFONIC ACID To a 4 dram vial (reactor design 2) was added a mixture of fluorenone (0.40 g, 2.22 mmol, 1.00 equivalents) and phenol (2.10 g, 22.3 mmol, 10.0 equivalents) The capped vial was placed into the heating control block regulated at 63°C and stirring was begun. 2,3-Dimercaptopropanesulfonic acid (0.021 g, 0.011 mmol, 0.050 equivalents) was added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC (analytical method 2) . The 9-fluorenone was found to be 5 percent consumed in 1.5 hours. IL. 3-MERCAPTOPROPIONIC ACID AND METHANESULFONIC ACTD (COMPARATIVE EXAMPLE) To a 4 dram vial (reactor design 2) was added a mixture of fluorenone (0.460 g, 2.55 mmol, 1.00 equivalents) and phenol (5.00 g, 53.1 mmol, 20.8 equivalents) The capped vial was placed into the heating control block regulated at 55°C and stirring was begun. 3-Mercaptopropionic acid (0.0217 g, 0.204 mmol, 0.080 equivalents) and methanesulfonic acid (0.0197 g, 0.205 mmol, 0.080 equivalents) were added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 32 percent consumed within 30 minutes, 51 percent consumed within 1 hour, and 71 percent consumed within 2 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 71 percent conversion: % by area product 93.7 BHPF 5.5 2,4-isomer 0.8 two:three adduct % = percent E. 3-MERCAPTOPROPIONIC ACID AND METHYLSULFAMIC ACID (COMPARATIVE EXAMPLE) To a 4 dram vial (reactor design 2) was added a mixture of fluorenone (0.460 g, 2.55 mmol, 1.00 equivalents) and phenol (5.00 g, 53.1 mmol, 20.8 equivalents) The capped vial was placed into the heating control block regulated at 55°C and stirring was begun. 3-Mercaptopropionic acid (0.0217 g, 0.204 mmol, 0.080 equivalents) and methylsulfamic acid (Aldrich 98 percent) (0.0227 g, 0.204 mmol, 0.080 equivalents) were added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 13 percent consumed within 1 hour, and 21 percent consumed within 2 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 21 percent conversion: % by area product 95.4 BHPF 4.6 2,4-isomer n/d two:three adduct % = percent ΕA SUBSTITUTION OF PHOSPHONIC ACIDS FOR METHANESULFONIC ACID (COMPARATIVE EXAMPLES) The reaction conditions described in Example 5D were repeated substituting each of the following acids (each at 8 mole percent) for methanesulfonic acid in the reaction: sulfamic acid (Aldrich 98 percent) , methylphosphonic acid (Aldrich 98 percent) , and phenylphosphonic acid (Aldrich 98 percent) . In each case, very little conversion of the fluorenone was observed in comparison with the use of methanesulfonic acid. These examples demonstrate that mixtures of a mercapto-compound and an acid are inferior to 3- mercaptopropanesulfonic or 4-mercaptobutanesulfonic acid for catalyzing the condensation of phenol with fluorenone. EXAMPLE 6 EFFECT OF WATER CONCENTRATION IN FLUORENONE PHENOLATIONS TTSTNG MPSA WITH DIPHENYLMETHANE AS A CO-SOLVENT A. 9-Fluorenone (3.65 g, 0.0200 mole, 1.00 equivalents) , molten phenol (39.6 g, 0.420 mole, 20.8 equivalents) , deionized water (0.055 g, 3.06 mmol, 0.151 equivalents) and diphenylmethane (32.83 g) was added to the reactor (reactor design 2) . The reaction mixture was heated to 53°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.170 g, 1.10 mmol, 0.0537 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 53°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 49 percent consumed within 2 hours and 77 percent consumed within 4.5 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 77 percent conversion: % by area product 96.1 BHPF 3.4 2,4-isomer 0.5 two:three adduct % = percent B. 9-Fluorenone (3.65 g, 0.020 mole, 1.0 equivalents), molten phenol (39.6 g, 0.420 mole, 20.8 equivalents), deionized water (0.362 g, 20.1 mmol, 0.994 equivalents) and diphenylmethane (32.83 g) was added to the reactor (reactor design 2) . The reaction mixture was heated to 53°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.158 g, 1.00 mmol, 0.0500 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 53°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 25 percent consumed within 2 hours, 45 percent consumed within 4.5 hours, and 57 percent consumed within 6 hours. HPLC analysis (analytical method 3) gaves the following relative area percent analysis for the reaction products (fluorenone area not included) at 57 percent conversion: % by area product 96.3 BHPF 3.7 2,4-isomer n/d two:three adduct % __ percent C. 9-Fluorenone (3.65 g, 0.0200 mole, 1.00 equivalents) , molten phenol (39.6 g, 0.420 mole, 20.8 equivalents), deionized water (1.09 g, 60.7 mmol, 3.00 equivalents) and diphenylmethane (32.83 g) was added to the reactor (reactor design 2) . The reaction mixture was heated to 53°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.158 g, 1.00 mmol, 0.0500 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 53°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 11 percent consumed within 2 hours, 20 percent consumed within 4.5 hours, and 23 percent consumed within 6 hours. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the reaction products (fluorenone area not included) at 23 percent conversion: % by area product 95.9 BHPF 4.1 2,4-isomer n/d two:three adduct % = percent These examples show that addition of large amounts of water to the reaction mixtures retards the condensation reaction. EXAMPLE 7 REMOVAL OF WATER UNDER VACUUM WITH AND WTTHOTTT DIPHENYLMETHANE AS A CO-SOLVENT A. 9-Fluorenone (127.7 g, 0.709 mole, 1.00 equivalents) and molten phenol (996.1 g, 10.58 mole, 14.9 equivalents) was added to the reactor (reactor design 4, 3 L) . The reaction mixture was heated to 45°C with stirring under a pad of nitrogen. 3-Mercaptopropanesulfonic acid (5.53 g, 35.4 mmol, 0.0500 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45 °C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 60 percent consumed within 1 hour, 88 percent consumed within 2 hours, and 95 percent consumed within 2.5 hours. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the reaction products at 100 percent conversion: % by area product 98.0 BHPF 1.4 2,4-isomer 0.7 two:three adduct % = percent B. 9-Fluorenone (127.7 g, 0.709 mole, 1.00 equivalents) and molten phenol (996.4 g, 10.59 mole, 14.9 equivalents) was added to the reactor (reactor design 4, 3 L with a Dean-Stark water separation trap and vacuum inlet attached in lieu of the nitrogen inlet) . The reaction mixture was heated to 45°C with stirring. 3-Mercaptopropanesulfonic acid (5.53 g, 35.4 mmol, 0.0500 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45°C. The reaction mixture was allowed to stir for 15 minutes at atmospheric pressure, then vacuum was applied to the reactor. From this point on, the reaction was conducted under reduced pressure conditions (<5 mm Hg) with water/phenol distillate collected in the Dean-Stark trap. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 68 percent consumed within 1 hour, 98 percent consumed within 2 hours, and 100 percent consumed within 2.5 hours. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the reaction products at 100 percent conversion: % by area product 98.1 BHPF 1.3 2,4-isomer 0.6 two:three adduct % = percent C. 9-Fluorenone (191.5 g, 1.063 mole, 1.00 equivalents), molten phenol (1500 g, 15.9 mole, 15.0 equivalents) and diphenylmethane (156.7 g) were added to the reactor (reactor design 4, 3 L with a Dean-Stark water separation trap and vacuum inlet attached in lieu of the nitrogen inlet) . The reaction mixture was heated to 45°C with stirring. 3-Mercaptopropanesulfonic acid (8.27 g, 53.0 mmol, 0.0499 equivalents) was added slowly over approximately 1 minute to the reaction mixture at 45°C. The reaction mixture was allowed to stir for 15 minutes at atmospheric pressure, then vacuum was applied to the reactor. From this point on, the reaction was conducted under reduced pressure conditions (<5 mm Hg) with water/phenol distillate collected in the Dean-Stark trap. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 20 percent consumed within 15 minutes, 80 percent consumed within 2 hours, 98 percent consumed within 3.5 hours, and 100 percent consumed within 6 hours. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the reaction products at 100 percent conversion: * by area product 98.3 BHPF 1.2 2,4-isomer 0.5 two:three adduct % __ percent These results show that removal of water from the reaction mixtures, containing diphenylmethane solvent, is unnecessary. These results show that removing water from the reaction mixtures accelerates the rate of the phenolation reaction, but is not necessary for good reaction rates and conversions. EXAMPLE 8 REACTION OF PHENOL WITH ACETONE TO PRODUCE BISPHENOL A USING MPSA CATALYST A. To a 4 dram vial (reactor design 2) was added a mixture of acetone (0.11 g, 1.8 mmol, 1.0 equivalents) and phenol (2.40 g, 25.5 mmol, 14.0 equivalents) . The capped vial was placed into the heating control block regulated at 62°C and stirring was begun. 3-Mercaptopropanesulfonic acid (0.021 g, 0.13 mmol, 0.070 equivalents) was added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The acetone was found to be approximately 70 percent consumed within 2 hours. HPLC analysis (analytical method 2) gave a relative area percent ratio of 97.0:3.0 for the desired reaction product 2, 2-bis- (4-hydroxyphenyl)propane (4,4-bisphenol A) relative to the isomeric impurity 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl) -propane (2,4-bisphenol A) at 70 percent conversion. B. To a 4 dram vial (reactor design 2) was added a mixture of acetone (0.11 g, 1.8 mmol, 1.0 equivalents) and phenol (2.40 g, 25.5 mmol, 14.0 equivalents) . The capped vial was placed into the heating control block regulated at 25°C and stirring was begun. 3-Mercaptopropanesulfonic acid (0.074 g, 0.47 mmol, 0.25 equivalents) was added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The acetone was found to be approximately 70 percent consumed within 2 hours. During the later stages of reaction, the reaction product began to crystallize from the reaction mixture. HPLC analysis (analytical method 2) gave a relative area percent ratio of 98.9:1.1 for the desired reaction product 2,2-bis- (4-hydroxy-phenyl)propane (4,4-bisphenol A) relative to the isomeric impurity 2- (2-hydroxyphenyl) -2- (4-hydroxyphenyl)propane (2, 4-bisphenol A) for the bulk reaction solution. Separation of the crystalline product from the reaction mixture followed by rinsing of the crystals with water to remove surface impurities provided 4,4-bisphenol A product containing less than 500 parts per million of the 2,4-bisphenol A impurity. C. (Comparative Example) To a 4 dram vial (reactor design 2) was added a mixture of acetone (0.11 g, 1.8 mmol, 1.0 equivalents) and phenol (2.40 g, 25.5 mmol, 14.0 equivalents) . The capped vial was placed into the heating control block regulated at 62°C and stirring was begun. 3-Mercaptopropionic acid (0.014 g, 0.13 mmol, 0.070 equivalents) and methanesulfonic acid (0.013 g, 0.13 mmol, 0.070 equivalents) were added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The acetone was found to be approximately 70 percent consumed within 2 hours. HPLC analysis (analytical method 2) gave a relative area percent ratio of 96.2:3.8 for the desired reaction product 2, 2-bis- (4-hydroxyphenyl)propane (4,4-bisphenol A) relative to the isomeric impurity 2- (2-hydroxyphenyl) -2- (4-hydroxy-phenyl)propane (2,4-bisphenol A) at 70 percent conversion. These experiments show that MPSA gives a product, with a higher 4,4-isomer ratio than prior art catalysts. EXAMPLE 9 PREPARATION OF THE POLYMER-SUPPORTED MERCAPTOSULFONIC ACTD CATALYST (PMBSA) -. PREPARATION OF SULTONE INTERMEDIATE 1,4-Butanesultone (3.00 g, 22.0 mmol, 1.00 equivalent) was added to dry THF (150 mL) under a nitrogen atmosphere. The solution was cooled to -78°C using a dry ice/acetone bath. n-Butyllithium (1.6 molar in hexanes, 13.8 mL, 1.00 equivalent) was added slowly dropwise to the -78°C solution via an addition funnel over approximately 40 minutes with vigorous stirring. The homogeneous reaction mixture was allowed to stir for an additional 10-15 minutes at -78°C. Poly(vinylbenzylchloride) (3.3 g, approximately 1.0 equivalent of chloromethyl groups, 60/40 mixture of 3- and 4-isomers, Aldrich Chemical Co.) in dry THF (10 mL) was added over approximately 2 minutes to the reaction mixture at -78°C. The reaction mixture was allowed to slowly warm to room temperature in the cooling bath over approximately 3 hours. A white precipitate formed in the reaction mixture during the reaction period and remained as a solid as the mixture reached room temperature. Water (100 mL) was added to the reaction mixture and the white (insoluble) solid was removed by filtration under vacuum. The solid was slurry-washed with water, then with small volumes of methanol and methylene chloride and dried in a vacuum oven, providing 4.77 g of a white solid sultone-functional polymer. B ^ . CONVERSION OF THE SULTONE-FUNCTIONAL POLYMER TO POLYMER-SUPPORTED MERCAPTOSULFONIC ACID (PMBSA) The sultone-functional polymer from above (4.00 g, approximately 15.9 mmol sultone) was added to THF (125 mL) . Potassium thioacetate (2.20 g, 19.0 mmol, 1.20 equivalent) was added as a solid to the slurry of the polysultone in THF. One drop of 50 percent tetrabutylammonium chloride was added to the rapidly stirred slurry. The temperature rose to 26°C over several minutes, then slowly dropped to 20°C. Two additional drops of 50 percent tetrabutylammonium chloride were added and the solution was warmed to 40°C for 15 minutes. Water (100 mL) was slowly added over 1 hour to the reaction mixture at 40°C. Substantial solid remained in the mixture at all stages of the reaction. The water/THF reaction mixture was allowed to react 15 hours at 40°C. The solvent was removed by rotary evaporation and the resultant solid was ground to a fine powder. THF (125 mL) was again added to the solid, forming a slurry. Additional potassium thioacetate (2.20 g, 19.0 mmol, 1.20 equivalent) was added, resulting in an exotherm to 26°C. Several drops of 50 percent tetrabutylammonium chloride were added and the reaction mixture was heated to 40°C for 15 hours. The solvent was removed by rotary evaporation. The tan solid was slurried in a 2:1 (by volume) mixture of toluene/ethanol. Concentrated hydrochloric acid (50 mL) was added and the mixture was stirred at room temperature overnight. Most of the HCl was removed by sparging the mixture with nitrogen, then the solvents were removed by rotoevaporation. The light tan solid was slurry-washed extensively with 10 percent hydrochloric acid and with water. Drying overnight in a vacuum oven (60°C/full vacuum) provided 4.18 g of the polymer-supported mercapto¬ sulfonic acid as a light tan solid designated as PMBSA. £__. PREPARATION OF A GEL PMBSA CATALYST (PMBSA-MER) A catalyst was prepared as above, starting with Merrifield resin (200-400, 2 percent crosslinked, gel) , treated with butanesultone. The product is identified as PMBSA-MER. D. PREPARATION OF CATALYST FROM BROMOMETHYLATED MACROPOROUS POLYSTYRENE (PMBSA-XEBR) A catalyst was prepared as above, starting with bromomethylated Amberlite™ XE-305 macroporous resin (4 percent crosslinked, 20-50 mesh, 3.7 meq Br/g) . ^ . PREPARATION OF CATALYST FROM CHLOROMETHYLATED MACROPOROUS POLYSTYRENE (PMBSA-XECL) A catalyst was prepared as above, starting with chloromethylated Amberlite™ macroporous resin (4 percent crosslinked, 20-50 mesh, 4.3 meq Cl/g) . E m . PREPARATION OF CATALYST FROM MERRIFIELD RESIN AND 1.3-PROPANESULTONE (PMPSA-MER) Catalyst was prepared above, by treating Merrifield resin (2 percent crosslinked, 200-400 mesh, 4.3 meq Cl/g) with lithiated 1, 3-propanesultone, which can be prepared in accordance with T. Durst et a., . "A new route to 5- and 6-membered ring sultones," Can. J. Chem. , vol. 48 (1970) , pages 845-851. EXAMPLE 10 EVALUATION OF A MERCAPTOSULFONIC ACID POLYMER (PMBSA) TN THE REACTION OF PHENOL WITH FLUORENONE A. To a 4 dram vial equipped with a stirring bar (reactor design 2) was added 4.33 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the mercaptosulfonic acid polymer (PMBSA) prepared as in Example 9B. The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 36°C for 3 hours. To increase the rate of reaction the temperature was increased to 50°C for 18 hours. Monitoring of the reaction by HPLC showed some reaction at 36°C and 100 percent conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 18 hours of reaction (100 percent conversion) : % by area product 98.-86 BHPF 0 . 98 2 , 4 -isomer 0 . 16 two : three adduct % •_- percent TM B. (Comparative Example) Dowex 50WX4 (a crosslinked sulfonated polystyrene resin, The Dow Chemical Company) promoted with 2,2-dimethylthiazolidine (25 percent of the resin sulfonic acid equivalents) was washed on a glass filter frit with phenol at 55°C to remove water. The resin was then washed with a mixture consisting of a 20.8 : 1 mole ratio mixture of phenol to fluorenone at 55°C to displace the original phenol wash. To a 4 dram vial equipped with a stirring bar (reactor design 2) was added 2.13 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone and 0.74 g (35 percent by weight of the reactant solution) of the promoted Dowex 50WX4 catalyst activated as described above. The weight of catalyst used was determined after the reaction by recovery of the resin from the reaction mixture by filtration, washing the resin with toluene and hexane, and drying to a constant weight in a vacuum oven at 50°C for 6 hours. The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 18 hours. Monitoring of the reaction by HPLC showed approximately 17 percent conversion after 4 hours and 73 percent conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 18 hours of reaction (73 percent conversion) : % by area product 91.32 BHPF 6.78 2,4-isomer 1.90 two:three adduct % = percent C. (Comparative Example) To a 4 dram vial equipped with a stirring bar (reactor design 2) was added 2.16 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone and 0.34 g (16 percent by weight of the TM reactant solution) of dry Amberlyst 15 (a crosslinked sulfonated polystyrene resin available from Rohm and Haas Company) . The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 18 hours. Monitoring of the reaction by HPLC showed approximately 24 percent conversion after 4 hours and 64 percent conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 18 hours of reaction (64 percent conversion) : H by area product 95.82 BHPF 3.93 2,4-isomer 0.25 two:three adduct % = percent These experiments show that use of the catalysts disclosed herein gives higher conversions of fluorenone and higher 4,4/2,4-isomer ratios than the prior art catalysts. EXAMPLE 11 RECOVERY AND RECYCLING OF SOLID CATALYST (PMBSA) A. CATALYST RECOVERY The reaction mixture from Example 10A was cooled to 40°C and the mixture was centrifuged. The upper liquid layer was decanted and additional warm (40-45°C) 20.8 : 1 mole ratio phenol/fluorenone solution (approximately 3-4 times the catalyst volume) was added. The mixture was stirred, centrifuged, and the warm liquid layer was decanted. This wash procedure was repeated for a total of three washes, then the required amount of phenol/fluorenone reactant mixture was added and the reaction was begun. B ^ . FIRST RECYCLE To the 4 dram vial containing the mercaptosulfonic acid polymer recovered (as described above) from Example 11A was added 4.33 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone. The mixture was heated to 50°C for 4 hours. Monitoring of the reaction by HPLC showed approximately 90 percent conversion after 4 hours at 50°C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 4 hours of reaction (90 percent conversion) : % by area product 98.77 BHPF 1.09 2, 4-isomer 0 . 14 two:three adduct % = percent C . SECOND RECYCLE To the 4 dram vial containing the mercaptosulfonic acid polymer recovered (as described above) from the first recycle was added 4.00 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone. The mixture was heated to 50°C for 18 hours. Monitoring of the reaction by HPLC showed approximately 83 percent conversion after 4 hours and 100 percent conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 18 hours of reaction (100 percent conversion) : % by area product 98.79 BHPF 1.10 2,4-isomer 0.11 two:three adduct % = percent D. THIRD RECYCLE To the 4 dram vial containing the mercaptosulfonic acid polymer recovered (as described above) from the second recycle was added 2.00 grams of a 20.8 : 1 mole ratio mixture of phenol to fluorenone. The mixture was heated to 40°C for 18 hours. Monitoring of the reaction by HPLC showed approximately 90 percent conversion after 4.5 hours and 100 percent conversion after 18 hours at 40° C. HPLC analysis (analytical method 2) gave the following relative area percent analysis for the products after 18 hours of reaction (100 percent conversion) : % of area product 99 . 08 BHPF 0 . 92 2 , 4 -isomer * two : three adduct % = percent * = not detectable These experiments show that the catalyst can be recycled repeatedly without loss of activity. EXAMPLE 12 COMPOSITE EXPERIMENTAL DETERMINATION OF PARAMETERS FOR THE CONDENSATION OF PHENOL WITH FLUORENONE MPSA. DIPHENYL¬ METHANE) Experiments are run in stirred isothermal batch reactors (reactor designs 2 or 3) to determine the effect of temperature, molar ratios of reactants and amount of MPSA on reaction rates and product distribution. Results are shown in Table I. Graphical analysis of the results in Table I showed that formation of 2,4-BHPF was related to the reaction temperature. As the temperature increased, the 2,4/4,4 ratio increased. In contrast, the phenol/Fn (Fluorenone) mole ratio had little effect on the 2,4/4,4 ratio. The yield of 2:3 adduct increased markedly as the ratio of phenol/Fn decreased from 15:1 to 2.5:1 and the reaction temperatures was increased from 25°C to 85°C. Graphical analysis of results for runs at 18 mole percent of MPSA, in terms of initial reaction rates (BHPF moles/L*hr) showed a marked rate increase in going from 25 °C to 85°C. Increasing the concentration of MPSA catalyst also gave the expected increase in the reaction rate. The phenol:fluorenone ratio also affected the reaction rate. It was believed that higher ratios of phenol to fluorenone were beneficial for condensations, run in a solvent, such as diphenylmethane. TABLE II PHENOL + Fn > BHPF Catalyst MPSA, Various Percent Fn in Solvents Analytical Method 2 - UV Detector *In solvent DPM = diphenylmethane DPM/MC « diphenylmethane + methylene chloride MBenzoate = methyl benzoate ClBenzene = chlorobenzene 2,4,6TMPh = 2,4,6-TrimethylPhenol - - approximately % = percent The results in Table I show that the 2,4/4,4 ratio stays constant as conversion increases, whereas the 2:3/4,4 ratio increases. The amount of MPSA catalyst was related to the amount of 2, 4-isomeric product formed. High 2,4/4,4 ratios at high concentrations of MPSA were probably related to a shift toward an acid-catalyzed reaction to produce relatively higher amounts of 2,4-isomer. EXAMPLE 13 EFFECTS OF SOLVENTS ON PRODUCT DISTRIBUTION AND CONVERSIONS Experiments were run in stirred tank batch reactors to determine whether use of a solvent was advantageous. Results of these experiments were shown in Table II. The use of a solvent did not appear to be advantageous. Comparison of a run using 10 percent DPM with neat run, at the same MPSA concentration, showed that reaction rates were higher for the neat run, although the DPM run uses 2.5 times more catalyst/Fn. Higher 2,4/4,4 and 2:3-adduct ratios for the reactions in DPM was another disadvantage. It is therefore preferred to run the condensations in excess phenol as solvent. EXAMPLE 14 EFFECTS OF TEMPERATURE. MPSA CONCENTRATION AND PHENO /FLUORENONE RATIOS ON PRODUCT DISTRIBUTIONS (EXCESS PHENOL AS SOLVENT) Reactions were done in isothermal stirred tank reactors as described above. Results were presented in Table III. These results demonstrated that increasing the amount of catalyst increased the 2,4/4,4 isomer ratio. Increasing the reaction temperature or decreasing the phenol/Fn mole ratio led to higher amounts of 2:3 adduct in the product mixture. EXAMPLE 15 RECOVERY AND RECYCLING OF MPSA FROM THE REACTION MIXTURES Runs of 100 mL to 1.5 L (reactor designs 3 and 4) were done to determine whether MPSA can be extracted from the neat BHPF reaction solution with water and recycled to subsequent runs. The effect of stirrer rpm on the time required for breaking a resulting emulsion were also investigated. Phenol was weighed and charged into the reaction vessel . Fluorenone was weighed and charged to the reaction vessel, followed by a weighed quantity of MPSA catalyst. TABLE in _ PHENOL + Fn > BHPF Catalyst MPSA, Neat Reactions - no solvent Analytical Method 2 - UV Detector Bun Temp . Mole Mole % Time 2 , 4 / 4 , 2 : 3/ 4 , 4 % I ME≤Δ 1 Molecular sieves used to remove water while reaction is taking place + more catalyst is added. 2 Fn added continuously over 43 min. 3 MSA (methanesulfonic acid) and MPA (mercaptopropionic acid) used instead of MPSA The concentrations of materials in the resulting mixtures were followed by HPLC (Analytical Method 4) . The following mixtures were used: % __ percent wt.% = weight percent To the reactor was added 200 mL of the mixture and 200 mL of water. The resulting mixture was stirred for 10 minutes. The phases were allowed to separate and the separation time noted. A sample (10 mL) of the organic phase was removed for analysis by HPLC and I. C. (ion chromatography) . The aqueous phase was retained for analysis. The extraction of the remaining organic layer was repeated, using an equal volume of water (190 mL) . At the end of the extraction and separation, 10 mL of the organic layer was retained. The remaining 180 mL of organic layer was extracted with 180 mL of water. A 10-mL sample of the organic layer was retained, as before. The aqueous extract was distilled under vacuum to give a solution of phenol, MPSA and small amounts of BHPF. Acid titration and I.C. analysis indicates that all of the MPSA was recovered from the mixtures. Results of representative extractions were given in Table IV. Table IV Extraction Data for Neat 21:1 (Phenol/Fn) Run (500 rpm Stirring Rate) Extraction 1 2 3 Phase Org . Aq . Org . Aq . Org . Aq . g. used 217 200 251.4 190 216.2 180 g. end 262.2 154.9 226.9 214.5 196.4 199.8 % Component in Phase Phenol 62.8 6.71 57.6 6.63 59.2 6.39 Fn 0.00 0.0 0.00 0.0 0.00 MPSA 0.08 0.55 0.030 0.12 0.0100 0.039 H 2 0 23.7 92.7 28.0 93.3 25.1 93.6 BHPF 13.4 0.0098 4.4 15.8 0.0073 percent (150 rpm Sti ring Rate) 2 3 Org . A . Org . Aq. 258 190 226.4 180 237.2 200.5 195.36 200.6 rcent Component in Phase 61.6 7.17 61.1 6.82 0.00 0.0 0.00 0.0270 0.10 -0.005 0.03 24.2 92.7 23.5 93.2 14.3 15.4 % = percent ** 4th and 5th extractions: equal volumes of organic and water layers: MPSA in organic 0.0030 (4th), 0.0005 (5th), in water 0.0143 (4th), 0.0025 (5th) EXAMPLE 16 TS MERIZATTON STUDY IN THE PRESENCE OF MPSA Reactions were done in stirred batch isothermal reactors (reactor design 2) . To the reactor was charged a mixture of 83.2 percent by weight of phenol, 0.09 percent by weight of fluorenone, 13.2 percent by weight of BHPF, containing 0.92 percent by weight of 2, 4-isomer and 0.68 percent by weight of 2:3 adduct. Various amounts of MPSA were charged to the reactor. The resulting mixtures were stirred and heated. The compositions in the reactor at various times were determined by analytical method 4. Compositions of other reaction mixtures were given in Table V. Results are given in Table VI. These results show that heating mixtures, in the presence of MPSA, brings about isomerization of the reaction mixtures toward higher concentrations of 9,9-bis- (4-hydroxyphenyl) -fluorene. The concentration of higher adducts also increases as a result of prolonged heating. EXAMPLE 17 PURIFICATION OF 9.9-BIS- (4-HYDROXYPHENYL) FLUORENONE A. PRECIPITATION FROM METHYLENE CHLORIDE A synthetic reaction mixture (105.5 g: 63 percent by weight, 66.5 g of phenol; 20 percent by weight, 21.1 g of 4,4-BHPF and 17 percent by weight, 18 g of water) was placed in a 500-mL round-bottom three-neck flask equipped with a heating mantle/Variac, thermometer, stirring bar and distillation arm. A temperature controller commercially available from Instruments for Research and Industry, Inc. under the trade designation Therm-O-Watch™ was used to control temperature of the liquid in the flask. A separate thermometer was placed in the distillation tower to monitor temperature in the vapor phase. The mixture was stirred and heated at ambient pressure up to a temperature of 160°C, during which time distillation of phenol and water occurred. Analysis of the reaction mixture indicated the phenol:BHPF mass ratio was 1:1. The reaction mixture, while still hot, was slowly added to 176 g of BHPF-saturated methylene chloride and the resulting mixture was slowly swirled to produce a homogeneous solution, clear and yellow in color. The mixture was allowed to cool to room temperature which causes crystallization to occur. The rod-like crystals present in the magma were analyzed by microscope prior to filtration. Approximately 80 percent of the crystals viewed were longer than 100 microns and had a diameter between 20 and 50 microns. The crystal magma was filtered on a medium porosity glass frit, using a vacuum produced by water jet. The filter cake was displacement-washed with 79 g of BHPF- saturated methylene chloride and then 72 g of hot (90°C) water. After drying at 65°C in air overnight, 12.9 g of white product was recovered. Isolated yield was 61 percent and HPLC purity was 99.8 percent. E ^ WASHING WITH SODIUM BICARBONATE SOLUTION Synthetic reaction mixture (105.5 g as in Example 17A) was combined with 100 mL of a 2 percent by weight aqueous solution of sodium bicarbonate. The mixture was agitated and then the organic and aqueous layers were allowed to separate in a separatory funnel. The organic layer was drawn off. This process was performed a total of 4 times. Washed reaction mixture (85.2 g: 58 percent, 58 g of phenol; 17.4 percent, 17 g of 4,4-BHPF and 25 percent, 21 g of water) was placed in the apparatus, described in Example 17A. The mixture was stirred and heated at a pressure of 80-100 mm Hg, (11-13 kPa) up to a temperature of 160°C, during which time distillation of phenol and water occurred. BHPF-saturated phenol (100 g) was then added to the reaction mixture and the temperature of the mixture was controlled at 65°C. Crystallization began within 1 h. The slurry was stirred overnight, after which the rod-like crystals present in the magma were analyzed by microscope before filtration. Approximately 30 percent of the crystals viewed had a length greater than 100 microns and a diameter between 10 and 30 microns. The crystal magma was filtered on a medium porosity glass frit using a vacuum produced by water jet. The brown filter cake was displacement-washed with 200 mL of room-temperature water and then stir washed with the same amount of water. The brown/beige crystals were then washed with BHPF-saturated methylene chloride and then with ethylene dichloride. After drying at 65°C in air overnight, 7 g of brown product were recovered. The isolated yield was 47 percent and HPLC purity was 99.7 percent. C . DISTILLATION OF PHENOL, CRYSTALLIZATION FROM TOLUENE Synthetic reaction mixture (149 g: 17.5 percent by weight, 24 g of 4,4-BHPF; 95 g of phenol and 30 g of water) were charged to the reactor, described in Example 17A. The mixture was stirred and heated at a pressure of 80-100 mm Hg up to a temperature of 160°C, during which time distillation of phenol and water occurred until the phenol:BHPF mass ratio was reduced to approximately 1:1. There was no increase in adduct concentration. The resulting mixture was added while still hot to 121 g of BHPF-saturated toluene. The resulting homogeneous solution was allowed to cool to room temperature, during which crystallization occurred. The resulting rod-like crystals present in the magma were analyzed by microscope prior to filtration. Approximately 20 percent of the crystals viewed had a length greater than 100 microns and a diameter between 10 and 50 microns. The crystal magma was filtered on a medium porosity glass frit using a vacuum produced by water jet. The pink filter cake was treated similarly to other examples. After drying at 65°C in air overnight, 18.5 g of pink product were recovered. Isolated yield was 77 percent and HPLC purity was 98.1 percent. ∑ _. DISTILLATION OF PHENOL; CRYSTALLIZATION FROM METHYLENE CHLORIDE Phenol and fluorenone were combined in the presence of 3-mercaptopropanesulfonic acid (MPSA) to produce a reaction mixture which, after washing to remove the acid catalyst, contained 20 weight percent of 4,4-BHPF, 64 weight percent of phenol and 16 weight percent water. The reaction mixture was distilled under water jet vacuum (approx. 80 mm Hg) up to a temperature of 160°C to yielded a residue, containing approximately 50 weight percent of phenol and 50 weight percent of 4,4-BHPF, i.e., a 1:1 phenol:4,4-BHPF mass ratio. The 1:1 mixture was cooled to 120°C and then poured into 176 g of room temperature methylene chloride, that had been previously saturated with 4,4-BHPF. This resulted in a clear homogeneous solution at reflux, which was allowed to cool to room temperature. The crystallized mixture was filtered under vacuum at room temperature. The filter cake was displacement washed with 79 g of BHPF- saturated methylene chloride (no stirring of the filter cake during the wash) and then stir-washed with 72 g of hot water (90°C) . The resulting white filter cake was dried in air at 60°C to provide a yield of 61 weight percent of the 4, -BHPF originally detected in the reaction mixture. E. REMOVAL OF PHENOL-WATER AZEOTROPE Approximately 380 g of a reaction mixture similar to that of Example 17D were slowly dripped into 4 L of water at a temperature of 84°C at a pressure of 300 mm Hg. This dilution in water was accompanied by the removal of phenol in the form of a water/phenol azeotrope. The water- insoluble materials then precipitated from the liquid phase as a white powder. Approximately 64 g of "crude" BHPF was obtained in this manner. The "crude" BHPF contained all the impurities originally contained in the reaction mixture. The product was filtered, washed with boiling water and dried in air at 60°C to provide a recovery of 96 weight percent of the 4,4-BHPF originally detected in the reaction mixture. F. CRYSTALLIZATION FROM TRIISOPROPYLBENZENE A reaction mixture (55.8 g: 63.1 percent by weight, 35 g of phenol; 14 percent by weight of 4,4-BHPF and 23 percent by weight, 12.8 g of water) was charged to a 250- mL round bottom flask, otherwise fitted out as in Example 17A. Triisopropylbenzene (TIPB, 106.6 g) was added to the mixture in the flask, as a result of which the mixture separated into two phases, of which the yellow reaction mixture was the lower. The mixture was stirred and heated under vacuum, produced by a water jet (ca. 80 mm) . After removal of water at 50-88°C, the mixture appeared homogeneous. The mixture was stirred and allowed to cool. Solids appeared when the temperature reached 70°C. The mixture was allowed to cool to room temperature and filtered on a glass frit under vacuum. The white solids on the frit were washed with TIPB. The filter cake was left overnight under vacuum (water jet) while air was pulled through the filter cake. Analysis of the resulting mother liquor showed that little of the phenol in the feed was removed as a result of distillation. The filter cake contained 4.2 g of white, nearly free-flowing product (54 percent recovery, 98.8 percent purity by HPLC) . G. DISTILLATION TO REMOVE PHENOL; CRYSTALLIZATION FROM METHYLENE CHLORIDE A reaction mixture (98.8 g: 61 percent by weight, 60.3 g of phenol; 19.4 percent by weight, 19.2 g of 4,4- BHPF and 19.6 percent by weight, 19.4 g of water) was charged to an apparatus, described in Example 17F. A collection flask was attached to the distillation arm and connected to a vacuum source (water jet) . The temperature set point was adjusted to 100°C and heating was begun. Tsmp . (°C) Observations/Actions 50 - 55 boiling and distillation occur 100 slight bubbling set point raised to 120°C 105 distillation restarts 115 insignificant distillation set point raised to 140 C C 120 vigorous boiling, little distillation, vapor temperature rising 121 vigorous boiling, distillation starting, vapor temperature 115°C 122 vapor temperature 118°C break vacuum and remove sample: 34 g of distillate collected, mixture in pot had phenol:BHPF mass ratio of ca. 2:1 reconnect vacuum source and recommence heating 124 vapor temperature was 119°C, distillation starts 125 vapor temperature was 119°C break vacuum and sample mixture 13.9 g of distillate collected set point 120°C at atmospheric pressure reconnect vacuum and recommence heating phenol:BHPF 1.6:1 mass ratio in pot 129 vapor temperature 121°C distillation starts 131 vapor temperature 123°C stop operation, remove sample 42.4 g remain in pot; mixture in pot had phenol:BHPF ratio ca. 1.12:1; 6.7 g of distillate collected The pot residue at 110°C was added to 172 g of fresh drum-grade methylene chloride in a bottle. The addition was done slowly in order to avoid excessive flashing or boiling of the methylene chloride. The resulting mixture more or less separated into two layers, of which the upper layer was richer in the phenol:BHPF component. The mixture was swirled and became homogeneous. The bottle was sealed and placed in a pan of cold water (ca. 10°C) . Time Observations/Actions (hr-.min. ) 0 : 08 homogeneous yellow solution 0 : 18 homogeneous yellow solution 0 : 56 yellow solution, possibly small crystals l : 18 same 2 : 00 same 2 : 24 crystallization ongoing, quite a few crystals 17 :48 solid yellow crystalline mass breaks up easily filter under vacuum through glass frit to obtain slightly yellow crystals ; recover 158 .8g of yellow mother liquors The crystallizer bottle was rinsed with 29.7 g of fresh methylene chloride (not all solids dissolve) , the resulting mixture being used to displacement wash the filter cake , which improved slightly in color . The filter cake was slurry washed with 49.4 g of fresh methylene chloride and the resulting slurry was filtered under vacuum. The color of the filter cake was unchanged . The filter cake was displacement washed with 33 g of cold water, without a change in the color of the cake . The filter cake was slurry washed with 40 g of boiling water, without a change in the color of the cake . The cake was dried in air under vacuum for 2 hours, transferred to a watch glass and dried in an oven overnight at 65°C. The cake was slightly yellow. The mass balance for the process is : g of BHPF 19.2 in initial mixture 8.1 in mother liquors at end of operation 9.1 isolated product 1.7 in wash 0.3 unaccounted for L__ CRYSTALLIZATION FROM DIPHENYLMETHANE 1. A mixture of 28 g of DPM, 17.5 g of phenol, 5.4 g of BHPF (98:2 4,4- to 2,4- isomers, by HPLC) and 12 mg of MPSA was washed with water. The resulting layers were separated and the water layer was removed. Phenol was distilled from the organic layer to give a mixture containing 21.8 g of DPM, 3.8 g of phenol and 5.4 g of BHPF. The mixture was cooled to room temperature to give an off-white precipitate, which was filtered and washed with DPM. The washed cake was dried in an oven at 60°C to give 6.1 g of material, containing 70 percent by weight of BHPF and 30 percent by weight of phenol. The mixture was stripped at 140°C under nitrogen at < 80 mm Hg (llkPa) to give 4.2 g of white solid. The solid, by HPLC analysis (analytical method 5), contains 99.6 percent by area of the 4,4-isomer and 0.04 percent by area of 2,4-isomer. 2. A reaction mixture from 15:1 phenol:fluorenone, containing 34.5 percent by weight of phenol and 10.5 percent by weight of BHPF, was diluted with 55 percent by weight of DPM. Phenol (80 percent of that initially present, maximum temperature 105°C, 4.5 mm Hg (0.6 kPa) ) was removed by distillation to give, after crystallization from DPM, white BHPF melting at 221-222°C. The recovery of BHPF was 78 percent. The material contains area 99.6 percent of the 4,4-isomer by HPLC. ∑___ CRYSTALLIZATION FROM NEAT PHENOL Phenol was distilled from the reaction mixtures to produce mixtures, containing less than 50:50 phenol:BHPF by weight . The resulting materials could be washed with methylene chloride. The products were inconsistent in color and contained small crystals, usually of the order of 10-70 microns. J. PRECIPITATION OF BHPF BY ADDITION TO WATER Addition of reaction mixtures to boiling water or steam removed some phenol as a phenol-water azeotrope. The resulting product retained most of the extraneous isomers and adducts and comprised very small crystals, of the order of 10-20 microns. The maximum purity was of the order of 97-98 percent. Analytical data (HPLC) are given in Table VII for samples, prepared in accordance with the practice of the invention and for commercially-available materials. Km. REMOVAL AND RECOVERY OF PHENOL FROM BHPF REACTION MIXTURE Excess phenol was removed from a reaction mixture to a 1:1 ratio of phenol:BHPF using a falling film evaporator. This was accomplished at 120°C/120 mm Hg. At this temperature, BHPF solubility in phenol was 45 percent. After removing phenol, the BHPF-phenol mixture was kept at 90°C and stirred prior to addition of methylene chloride or other crystallizing solvent. BHPF was crystallized at room temperature under a nitrogen pad. A batch crystallizer was cooled to 5-10°C for several hours during which BHPF crystallized. Solid BHPF was separated from the resulting slurry using a batch pressure filter or basket filter. Optionally, a pressure filter could be used. Methylene chloride or other solvent can be recycled to the process. BHPF crystals were dried under vacuum. COMPARATIVE MATERIALS BHPF from Sloss (Birmingham, Alabama) : The sample evaluated was a dry solid, from lot number 9307-03. BHPF from Isonova (Austria) : The sample evaluated was designated "Isonova 10/93". BHPF from Rutgers Nease (State College, Pennsylvania) : The dry solid was from lot number 9306099. BHPF from Isovolta (Neudorf, Austria) : The sample, used as standard for the comparative studies, was received in 1988 and was designated "Isovolta 1988." Analysis of the results in Table VII shows that 4,4- BHPF, purified by distillative removal of phenol:water azeotrope and extraction with methylene chloride, produced high purity BHPF. Corrosion tests were performed using a representative reaction mixture for the condensation of phenol with fluorenone using various catalysts. The tests were done using metal specimens 3.81 cm in length, 1.59 cm in width, 0.32 cm thick, and having a 0.64 cm hole centered in one end. The specimens were isolated from each other and the mounting rack using polytetrafluoroethylene shoulder washers. The specimens were exposed to both the liquid and vapor phases of each test cell. The contents of the cells were stirred continuously and were maintained at the selected temperature using temperature controllers and heating mantles. The tests were run under a nitrogen pad. The chloride content of the test mixtures was <500 ppm. The tests were run at 65°C for 13 days (312 h) . Compositions tested and results were presented in Table VIII. Results in Table VIII demonstrate that the reaction mixtures used were considerably less corrosive than conventionally used reaction mixtures. TABLE VTII CORROSION TESTING FOR BHPF REACTION MIXTURES A. Reactor Mixture: 90.2 percent of Phenol, 8.3 percent of Fluorenone, 1.5 percent of MPSA (by weight) Corrosion Rate (mpy) * Metal + Liquid Vapor Remarks 316L ss** nil*** < 0.1 uniform corrosion 904L ss nil 0.1 uniform corrosion 2205 ss nil < 0.1 uniform corrosion 254 SMO ss nil nil uniform corrosion B. Water Extraction Mixture: 8.0 percent of Phenol, 91 percent of Water and 1.0 percent of MPSA (by weight) Corrosion Rate (mpy) Metal + Liquid Vapor Remarks 316L ss 0.1 0.1 uniform corrosion 9041* ss < 0.1 < 0.1 uniform corrosion 2205 ss < 0.1 < 0.1 uniform corrosion 254 SMO ss < 0.1 < 0.1 uniform corrosion C. Recycle Concentrate: 29.87 percent of Phenol, 69.23 percent of Water and 0.9 percent of MPSA (by weight) Corrosion Rate (m ) * mpy = mils per year; 1 mpy = 0.00254 cm/yr ** ss = stainless steel *** nil = < 0.01 mpy ± All metal compositions as defined by the American Trnn and Steel Institute R, REACTION MIXTURES FOR BISPHENOL A PROCESS A mixture containing 94.35 percent by weight of phenol, 4.15 percent by weight of acetone and 1.50 percent of MPSA was evaluated as in Example 18A. The following results were obtained: pass = < 0.00254 cm/year + All metal compositions as defined by the American Iron and Steel Institute The corrosion rates in both the liquid and vapor phases was < 0.00254 cm/year. The corrosion was uniform. The rate of corrosion was below that for conventional reaction mixtures for making bisphenol A. EXAMPLE 19 m . PREPARATION OF BISPHENOL A USING PMBSA Bisphenol A was prepared from 14:1 phenol:acetone (mole ratio) at 50°C, containing the indicated amounts of solid catalyst. The product distribution was determined by analytical method 2. The PMBSA catalyst of Example 9B, at a level of 6 percent by weight, gave 75 percent conversion after 5 h. The product contained 99.0:1.0 of 4,4 :2,4-isomers (area percent) . The PMBSA was recovered and reused in a second cycle. The conversion after 4 h was 60 percent. The product contained 99.1:0.9 of 4,4 :2,4-isomers (area percent) . DOWEX™ 50WX4 (35 percent by weight as dry mass) , promoted with 25 percent by weight of 2,2- dimethylthiazolidine (DMT) , was used in a similar experiment. The conversion after 4 h was 43 percent and the product contained 98.0:2.0 (as area percent) of 4,4:2.4-isomers. These experiments show that a polymer-supported catalyst of this invention gives higher conversions and a higher yield of 4,4-isomer than a representative prior art catalyst. __. REACTION USING PMBSA IN A DOWNFLOW CONTINUOUS REACIΩB The reactor comprised a vertical tube. The bottom part of the tube was filled with glass beads, on top of which was provided a bed of PMBSA catalyst resin. The remainder of the tube was filled with glass beads. The tube was fitted with a pressure gauge, a pressure regulator, heating means external to the catalyst bed and feed means at the bottom of the tubular reactor for introducing the phenol and fluorenone reactants. The feed was prepared in a container, provided with a nitrogen stream and heated externally by a fluid. A valve was intermediate the feed preparation container and a pump for introducing the feed into the bottom of the reactor. A relief valve was placed between the pump and the reactor. The feed was introduced into the reactor at a predetermined rate and passes upwardly through the lower bed of glass beads, which functioned as a preheater, through the catalyst bed and the upper bed of glass beads, whereupon the product was removed from the top part of the reactor for analysis or further processing. Experiments using 21:1 phenol: fluorenone and PMBSA catalyst gave the following results as a function of flow rate and reaction temperature: Conversion (%) BHPF in phenol (%) Productivity (g BHPF/g cat/h) Selectivity (% 4,4-BHPF) Flow rate (g feed/g cat-h) % = percent These experiments show that lower reaction temperatures favor productivity and selectivity toward 4,4-BHPF, accompanied by decreased conversion. CONVERSION OF ACETONE AS A FUNCTION OF REACTION TEMPERATURE Phenol-acetone mixtures (6 percent by weight acetone) were converted to bisphenol A, using MPSA as catalyst in batch reactors. The following results were obtained (Table IX) : mixture contains 2.2 percent by weight of MPSA and 2-3 percent by weight of water mixture contains 1.3 percent by weight of MPSA and no added water IL. REMOVAL OF MPSA CATALYST USING ION-EXCHANGE RESTN: PURIFICATION OF CRYSTALLINE BISPHENOL A Condensation of phenol with acetone (4 percent by weight), containing 2 by weight of water, using 2.5 percent by weight of MPSA, was done at 35°C in plug flow mode, with a 3-h residence time. Crystallization of bisphenol A occurred in the reactor. The crystals were isolated by filtration and residual acetone in the mother liquors was recycled to the process at 50°C. The mother liquors were dried at 50°C (20 mm Hg) and the cycle was repeated after addition of make-up feed. 90 percent of the acetone was converted to bisphenol A per pass. Catalyst was removed from the product by first melting the crystals and washing the resulting oil with water, and then extracting the organic layer with water, which reduced the acid concentration below 100 ppm after three equilibrium stages. The remaining catalyst was removed using an anion exchange bed (<50 ppm, the limit of detection) . Bisphenol A, isolated by a single crystallization step, was of higher purity than products, generally obtained using two crystallizations. Bisphenol A isolated by a single crystallization, contained a maximum of 1200 ppm of 2,4-bisphenol. The process of this invention therefore simplifies the isolation of high purity of bisphenol A, uncontaminated by oily higher condensates. EXAMPLE 20 SOT.TD CATALYST PREPARED FROM POLYSTYRENE BY ALKYLATION WTTH ALLYL BROMIDE. SULFONATION AND THIOLATION A. Polystyrene commercially available from Rhom and Haas and Co. under the trade designation Amberlite™ XE 305 was alkylated with allyl bromide in the presence of trifluoromethanesulfonic acid in 1,2-dichloropropane at 50 °C, generally in accordance with Tomoi et al. , "A Novel One-pot Synthesis of Spacer-modified Polymer Supports and Phase-transfer Catalytic Activity of Phosphonium Salts Bound to the Polymer Supports," Reactive Polymers, vol. 3 (1985) , pages 341-349, to produce a material having 2- bromo-1-methylethyl chains. This material was sulfonated, generally at the ortho-position with respect to the side chain, by treatment with chlorosulfonic acid. The resulting sulfonyl chloride was converted to a sodium salt by reaction with sodium bicarbonate. The material was converted to a corresponding thiol by reaction with sodium thioacetate and converted to a corresponding acid by acidic hydrolysis. Materials prepared correspond to 28 and 48 percent of alkylmercaptan functionality (designated herein as XEMSA) . B. The thus-prepared polymers (XEMSA) were used at a level of 6 percent by weight for reaction between phenol and fluorenone (20.8:1 mole ratio) at 50°C. Product composition was determined by analytical method 3. The polymer containing 28 percent of alkylmercaptan functionality gives 75 percent conversion after 5 h. The product distribution was 96.8:3.2 of 4, :2,4-isomers (area percent) . The product containing 48 percent of alkylmercaptan functionality gives 15 percent conversion after 2 h. The product distribution was 96.8:3.2 of 4,4 :2,4-isomers (area percent) . EXAMPLE 21 TN -TTU METHOD FOR PREPARING THE POLYMER-SUPPORTED MERCAPTOSULFONIC ACID CATALYST .PMBSA CLASS) : A. SULTONE ALKYLATION To a mixture of 1,4-butanesultone (30.0 g, 220.0 mmol, 1.00 equivalent) and poly(vinylbenzylchloride) (PVBC, 33.6 g, approximately 220 mmol, 1.00 equivalent) of chloromethyl groups) was added via a cannula dry tetrahydrofuran (600 mL) under a nitrogen atmosphere. The mixture was stirred at room temperature until a homogeneous solution was obtained. The solution was then cooled to -78°C using a dry ice/acetone bath, n- Butyllithium (2.5 molar in hexanes, 88.1 mL, 1.00 equivalent) was added slowly dropwise to the -78°C solution of 1,4-butanesultone and poly(vinylbenzylchloride) via an addition funnel over approximately 2.5 h with vigorous stirring. A white solid began to precipitate from the reaction mixture as the n- butyllithium addition was begun, with precipitation continuing throughout the n-butyllithium addition period. By the end of the addition, a large amount of white solid had formed within the reaction medium. The reaction mixture (slurry) was allowed to slowly warm to room temperature in the cooling bath (over approximately 3-4 h) and was allowed to stir at room temperature overnight . The white precipitate which had formed in the reaction mixture during the n-butyllithium addition period remained insoluble as the mixture reaches room temperature. The white (insoluble) solid was removed by vacuum filtration. The polymer could be washed with water or water could be added to the THF/polymer slurry prior to filtration. Addition of water sometimes resulted in increasing the time required for filtration. The solid was slurry-washed with THF, then with methanol and finally with methylene chloride (causing some swelling) . The solid was dried overnight in a vacuum oven to provide 53.4 g of a white solid sultone-functional polymer. B ^ . THIPLATION To the sultone-functional polymer from above (110.0 g from two combined batches, approximately 0.440 mole of sultone) was added nitrogen-saturated THF (500 mL) . In a separate reactor, a solution of lithium thioacetate was prepared by the dropwise addition of thiolacetic acid (49.8 g, 0.650 mole) to a slurry of lithium carbonate (24.2 g, 0.330 mole) in water (100 mL, nitrogen saturat¬ ed) . The lithium thioacetate solution was added slowly via cannula to the polymer/THF slurry at such a rate that the temperature did not rise above 35°C. The polymer swelled substantially during the lithium thioacetate addition. After the lithium thioacetate addition was complete, an additional 350 mL of water (nitrogen saturated) was added. The polymer swelled to a volume of approximately 1 L. The mixture was heated to 50°C, and was allowed to react overnight. The gel-like polymer was then filtered using a coarse glass-fritted funnel. The polymer was washed with water, then with methanol, then with methylene chloride, and finally with additional water. The polymer slurry sometimes filtered very slowly during the filtration process. In this case, the washing steps required approximately two days. After the washing steps, concentrated hydrochloric acid (300 mL, approximately 37 percent by weight in water) was added to the polymer. The polymer shrank in volume and the HCl solution was easily removed by filtration. More concentrated HCl (300 mL) was added to the filtered solid, and the mixture was allowed to stand at room temperature over 2 days. The polymer was then washed extensively with dilute HCl solution, followed by extensive water washes. The polymer was then washed with methanol and finally with dichloromethane. Drying overnight in a vacuum oven (60°C/full vacuum) provided the polymer-supported mercaptosulfonic acid. The product was identified as PMBSA-SU. £_. CONVERSION OF CROSSLINKED POLYSTYRENE RESIN TO MERCAPTOSULFONIC ACID POLYMER A commercially-available (Fluka Chemie AG) Merrifield resin (2 percent divinylbenzene, 200-400 mesh, approximately 4.3 mmol Cl/g , 51.2 g, 1.0 equivalent) was reacted with 1,4-butanesultone (1.05 equivalents) and n- butyllithium (1.0 equivalent) according to the procedure described above to provide a sultone-functional polymer (70.0 g) . Subsequent thiolation of the sultone polymer in a manner similar to that described above provided the corresponding mercaptosulfonic acid polymer (79.0 g dry mass) . This material was identified as PMBSA-MER. In this reaction sequence, the lithium thioacetate reagent was formed in situ by slowly adding solid lithium carbonate to a mixture of the sultone polymer and thiolacetic acid in a 3:2 volume ratio of nitrogen- saturated THF/water. EXAMPLE 22 PREPARATION OF POLYMER-SUPPORTED MERCAPTOSULFONIC ACTD CATALYST (XEMSA CLASS) ^ ALKYLATION OF POLYSTYRENE To Amberlite™ XE-305 (75.0 g, approximately 0.720 mole of styrene repeat units, 1.00 equivalent) was added 600 mL of 1,2-dichloropropane (PDC). The polymer was allowed to swell in the solvent overnight. 5-Bromo-l- pentene (75.3 g, 0.702 equivalent) and PDC (125 mL) were added to an addition funnel. The reactor contents (polymer slurry and 5-bromo-1-pentene solution) were evacuated and back-filled with nitrogen several times. Trifluoromethanesulfonic acid (20.0 g, 0.133 mole, 0.19 equivalent) was added to the polymer/PDC slurry. The slurry solution turned a dark amber color. The polymer slurry was heated to 45-50°C, and slow, dropwise addition of the 5-bromo-1-pentene solution was begun. The 5-bromo- 1-pentene solution was added slowly over approximately 3 days to the stirred polymer slurry at 50°C. After the 5- bromo-1-pentene addition was complete, the reaction was allowed to stir an additional 1 day at 50°C. The polymer slurry was very dark-colored throughout the addition period. The polymer slurry (very dark red-brown) was cooled to room temperature and filtered. The beads were washed extensively with dichloromethane (still dark colored beads) and then were washed extensively with water to remove most of the color. The beads were then washed with the following series of solvents: methanol, acetone, dichloromethane, acetone, and, finally, methanol. After drying in a vacuum oven at 60°C overnight, 96.46 g of nearly white bromoalkylated polymer beads were obtained. The mass uptake corresponded to a degree of functionalization (DF) of approximately 0.20. ______ SULFONATION To the dried bromoalkylated polymer beads prepared above (approximately 0.720 mole of styrene repeat units) was added 650 mL of dichloromethane under a nitrogen atmo- sphere. The polymer slurry was cooled to 0°C using an ice/water bath. Chlorosulfonic acid (258.2 g, 2.22 mole, 3.08 equivalents) was added slowly dropwise to the polymer slurry at 0°C over 2 h 40 min. The polymer beads turned copper-colored during the chlorosulfonic acid addition. After the addition was complete, the reaction mixture was allowed to slowly warm to room temperature within the water bath. The volume of the swollen polymer was approximately 500-600 mL within the reactor. After warming to room temperature, the polymer slurry was allowed to stand overnight without stirring. The liquid layer was then removed from the polymer using a small-bore cannula. The beads were then washed several times with dichloromethane. (The liquid layer and dichloromethane washes were slowly and carefully quenched in a separate vessel using ice.) The polymer beads were then carefully transferred to a fritted-glass funnel, and the polymer beads were quenched by slow, careful addition of ice water. After the beads were washed extensively with water, excess solid sodium bicarbonate was slowly added to a suspension of the polymer beads in water. The mixture was allowed to stand overnight at room temperature. The polymer/sodium bicarbonate mixture was then heated to 50°C for 2 h. The polymer slurry was allowed to stand at room temperature for 6 days. The polymer was light-colored and more highly swollen at this point. The slurry was heated to 50 °C and allowed to react overnight, giving a pH 4 solution of even more swollen polymer (approximately 600- 700 mL volume) . Addition of a small amount of sodium bicarbonate gave a pH 7 solution.. ζ_A THIOLATION To the aqueous polymer bead slurry from above was added sodium bicarbonate (60.5 g, 0.720 mole) . The mixture was evacuated and back-filled with nitrogen three times. Thiolacetic acid (41.1 g, 0.540 mole) was added slowly dropwise over 1 h 10 min to the polymer slurry at room temperature. The mixture was slowly warmed to 80°C over several h and allowed to react at 80°C for 3 days. After cooling to 40°C, the supernatant solution was removed using a small-bore cannula. The polymer was washed several times with water, giving slightly off-white colored polymer beads. Concentrated hydrochloric acid (250 mL) was added to the polymer and the slurry was heated to 50°C for 3 h. After cooling to room temperature, the hydrochloric acid solution was removed using a small-bore cannula. The polymer beads were then washed several times with dilute hydrochloric acid and the beads were transferred to a fritted-glass funnel. The beads were again washed repeatedly with dilute hydrochloric acid followed by extensive washings with water, giving slightly off-white water-swollen beads. (The water-swollen volume of the polymer beads was approximately 900 mL.) The beads were washed with methanol (methanol-swollen volume approximately 600 mL) and finally with dichloromethane. After being dried in a vacuum oven at 60°C overnight, the dark-colored beads had a dry volume of approximately 200 mL. This product is identified herein as XEMSA-5C. D. PREPARATION OF CATALYST FROM POLYSTYRENE AND 11- BROMO-1-UNDECENE (XEMSA-11C) Catalyst was prepared as above, starting with macroporous polystyrene (Amberlite™ XE-305) and 11-bromo- 1-undecene. EXAMPLE 23 EVALUATION OF POLYMERIC MERCAPTOSULFONIC ACID CATALYSTS A. EVALUATION OF THE MERCAPTOSULFONIC ACID POLYMER .XEMSA-5C) IN THE REACTION OF PHENOL WITH FLUORENONE To a 4 dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio mixture of phenol to fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the mercaptosulfonic acid polymer (XEMSA-5C) prepared as described in Example 22A-C. The reaction mixture consists of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 5 h. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 36 percent consumed within 2 h and 76 percent consumed within 5 h. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the products after 5 h of reaction (76 percent conversion) : 9,9-bis- (4-hydroxyphenyl)fluorene (97.45 area percent) : 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene (2.17 area percent) : adduct containing two fluorene units and three phenolic units (0.39 area percent). B ^ EVALUATION OF THE MERCAPTOSULFONIC ACID POLYMER .XEMSA) IN THE REACTION OF PHENOL WITH FLUORENONE To a 4 dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio mixture of phenol to fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the mercaptosulfonic acid polymer (XEMSA, degree of functionalization approximately 0.28 from bromoalkylation step) prepared as described in Example 20. The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 5 h. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9- fluorenone was found to be 44 percent consumed within 2 h and 75 percent consumed within 5 h. HPLC analysis (analytical method 3) gave the following relative area percent analysis for the products after 5 h of reaction (75 percent conversion): 9,9-bis-(4- hydroxyphenyl)fluorene (96.10 area percent) : 9- (2- hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene (3.52 area percent) : adduct containing two fluorene units and three phenolic units (0.38 area percent). £___ EVALUATION OF MERCAPTOSULFONIC ACID POLYMER .PMBSA-MER) IN THE REACTION OF PHENOL WITH FLUORENONE To a 4-dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio of phenol :fluorenone and 0.26 g (6 percent by weight of the reaction solution) of PMBSA-MER of Example 21C. The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymeric catalyst phase. The mixture was heated at 50°C for 2 hours. The reaction was monitored by collecting samples, which were analyzed by HPLC. The 9- fluorenone was 99.5 percent consumed within 2 hours. The product after 2 hours contained 96.83 area percent of 9,9- bis- (4-hydroxyphenyl) fluorene, 2.44 area percent of 9- (2- hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene and 0.72 area percent of an adduct containing two fluorene units and three phenolic units by HPLC (analytical method 3) . IL. EVALUATION OF MERCAPTOSULFONIC ACID POLYMER ■PMRSA-SU) FOR THE REACTION OF PHENOL WITH FLUORENONE To a 4-dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio mixture of phenol :fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the polymer of Example 2IB (PMBSA- SU) . The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 5 hours. The progress of the reaction was followed by HPLC. At the end of 2 hours, 67 percent of the fluorenone was consumed, and 85 percent at the end of 5 hours. At the end of 5 hours, the reaction mixture contained 97.09 area percent of 9, 9-bis- (4-hydroxyphenyl) fluorene, 2.25 area percent of 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene and 0.66 area percent of an adduct containing two fluorene units and three phenolic units by HPLC analysis. Results for the evaluation of various polymer mercaptosulfonic acids for condensing phenol with fluorenone are given in Table X. TABLE X CONVERSION OF FLUORENONE (percent (%)) USING 6 percent BY WETGHT OF POLYMERTC CATALYSTS AT 50°C Reaction time (h) Resin 0 2 4 5 7 18 PMBSA-MER 0 99.5 PMBSA-SU (PVBC) 0 67 85 PMBSA (PVBC) 0 66 XEMSA-5C 0 36 76 (Amberlite™ XE-305) XEMSA 0 49 75 82 (Amberlite™ XE-305) Dowex* 50 (DMT promoted) 0 17 73 *Trademark of The Dow Chemical Company. EXAMPLE 24 EVALUATION OF THE MERCAPTOSULFONIC ACID POLYMERS IN THE REACTION OF PHENOL WITH ACETONE To a 4 dram vial equipped with a stirring bar was added 4.33 g of a 14:1 molar ratio mixture of phenol to acetone and 0.26 g (6 percent by weight of the reactant solution) of the appropriate mercaptosulfonic acid polymer. The reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to and allowed to react at 50°C. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. HPLC analysis (analytical method 3) showed the following acetone percent conversion data (based upon the quantity of bisphenol A produced) for the different catalysts are given in Table XI : TABLE XI percent ACETONE CONVERSION .BASED UPON BISPHENOT, A PRODUCED) 5.0 75 82 32 ♦Trademark of The Dow Chemical Company DMT was 2,2-dimethylthiazolidine EXAMPLE 25 A. PREPARATION OF BHPF; METHYLENE CHLORIDE AZEOTROPE TO REMOVE WATER: PRECIPITATION FROM METHYLENE CHLORTDE: 5.75:1 MOLAR RATIO OF PHENOL TO 9-FLUORENONE.- COPRECIPTTATTON WITH TETRACHLOROETHYLENE To a reactor (isothermal stirred batch reactor; reactor design 4) was charged 75.0 g (0.80 mole) of phenol and 24.98 g (0.1386 mole) of 9-fluorenone. The mixture was heated to 40°C and catalyst (0.973 g, 0.0062 mole, 3- mercaptopropanesulfonic acid) was charged to the reactor. Heating was continued. The course of the reaction was followed by HPLC (analytical method 3) At 30 percent conversion, methylene chloride (15 g) was added to the reaction mixture so as to keep the mixture stirrable and to use a water/methylene chloride azeotrope (180 mm Hg, T = 37°C) to remove water of reaction. The reaction mixture was cooled at the end of the reaction (nearly complete fluorenone consumption, >99 percent of theoretical water) to increase the amount of crystalline precipitate. The progress of the run is given in Table XII. The reaction mixture (approximately 97 percent selectivity to 4,4-BHPF, little unreacted fluorenone) was split into two parts. The first fraction (53.3 g) was filtered. The filter cake was washed with methylene chloride (49 g) and then with hot water (55 g) . The recovery was 6.4 g (first crop) and 0.6 g (second crop) of white crystals, corresponding to 99 percent purity 4,4- BHPF (33 percent recovery) . To the remainder of the mixture (70.3 g) was added 61 g of tetrachloroethylene. The crystals were removed by filtration and the filter cake was washed with 50 g of tetrachloroethylene and then with 115 g of hot water. The recovered product weighed 11.5 g (43 percent recovery, 99 percent as 4,4-BHPF, white solid) . These results show that use of tetrachloroethylene, in combination with methylene chloride, gave higher recovery of 99 percent pure 4,4-BHPF) . TABLE XTT S Observation? . Actions Add MPSA; turns orange, then dark green brown Color light brownish Sample taken Seed crystal added Sample taken Methylene chloride (15 g) and see crystal added; no crystallization temp, raised to 45°C 2:30 37 -180 Sample taken; seed crystal not dissolving Heater set at 40°C Seed crystals added Mixture hazy Mixture hazy Sample taken Vacuum turned off, stirrer speed increased 9:30 40 760 Sample taken; methylene chloride (-20 g) added to mixture; stirrer speed increased; heater turned of - = approximately IL. USE OF METHYLENE CHLORIDE AZEOTROPE TO ACCELERATE REACTION: 5.75:1 MOLAR RATIO OF PHENOL TO 9-FLUORENONE To a reactor (reactor design 5) was charged 75.0 g (0.80 mole) of phenol, 24.98 g (0.1386 mole) of 9- fluorenone and 15.0 g of methylene chloride. The mixture was heated to 40°C. Catalyst (3-mercaptopropanesulfonic acid, 0.757 g, 0.0049 mole) was charged to the reactor and the mixture was stirred. The reaction was followed by HPLC (analytical method 3) . At the end of the reaction, methylene chloride was added to produce a mixture of 30 :30 :approximately 30 percent by weight of methylene chloride:BHPF:phenol and the mixture was heated to dissolve the crystalline material. Additional methylene chloride was added to the solution and the solution was cooled to promote crystallization. The progress of the reaction is shown in Table XIII. At the end of the reaction, half of the resulting mixture was filtered and the filter cake was washed with 64 g of methylene chloride. The first crop of BHPF weighed 7.0 g (dried overnight at 40°C) and was white with very little pink coloration. A second crop of crystals was collected and washed with 28 g of methylene chloride: weight, 4.1 g (dried overnight at 40°C, slightly pink) , 99 percent purity after a further washing with water. The remainder of the reaction mixture was filtered and the filter cake was washed with methylene chloride and hot water and dried overnight at 40°C. The recovery was 14 g (51 percent overall recovery) , 99 percent purity by HPLC. TABLE XIII mm. Hg Observations. Actions 760 Add MPSA, turns dark 760 Add 20 g of methylene chloride; color was dark brownish 0:30 45 760 Lighter brown; reduce pressure to approximately 180 mm 1:00 45 -180 Seed crystal added; no crystallization observed 2:00 45 -180 Seed crystal added; no crystallization observed 3:00 45 -180 Sample taken; seed crystal added; crystal not dissolving 3:45 45-> -180 Heater set at 40°C; crystals forming 4:00 40 -180 More crystals forming 6:30 40 Sample taken; solid crystalline mass; stirring ineffective; yellowish color; vacuum turned off 19:00 40 760 Sample taken; -50-70 percent of BHPF crystallized; 33 percent by weight of methylene chloride added; temperature increased to 58°C -20:30 58 760 Temperature lowered to <40°C; methylene chloride added to 80 percent make up by weight of mixture 24 760 Cooled to room temperature approximately £ , REACTION USING METHYLENE CHLORIDE AS SOLVENT: 3.5:1 MOLAR RATIO OF PHENOL TO FLUORENONE Phenol (30.0 g, 0.32 mole) , 9-fluorenone (16.41 g, 0.0911 mole) and 15.0 g of methylene chloride were charged to a reactor (reactor design 4) . The mixture was stirred and heated at 40°C and 1.122 g (0.0072 mole) of MPSA was added over approximately 1 min. Heating was continued at 41°C for the duration of the reaction. The following observations were made during the run: Time (h) HemC_. (°C) Observations. Actions 0 41 MPSA added; turns orange to brown to dark brown within 30 sec purple color sample taken sample taken orange mixture seeded with crystals sample taken; heater off; left overnight heater off sample taken; approximately 80 percent conversion; more 2:3 adduct than ,4 adduct The crystalline solid was removed by filtration and the filter cake was washed with methylene chloride. A second crop of crystals was recovered from the mother liquors. The yield was 0.86 g (first crop), 8.66 g (second crop) , 3.5 g (third crop), overall 13 g (41 percent) , >99 percent purity by HPLC (method 3) . C. PHENOL:FLUORENONE MOLAR RATIO OF 15:1; MPSA CATALYST: PHENOL REMOVED BY DTSTTLLATION: CRYSTAL TZED FROM METHYLENE CHLORIDE To a mixture of phenol and fluorenone (15:1 molar ratio), heated to 65°C, was added 0.0498 equivalent of 3- mercaptopropanesulfonic acid (with respect to fluorenone) . The resulting mixture was heated at 65°C for 2 h, after which the reaction mixture was washed with water (14 times the volume of the mixture) to remove MPSA. The washed reaction mixture was distilled to a phenol:BHPF weight ratio of 1:1 and cooled to bring about crystallization of BHPF. Crystalline material was removed by filtration, washed with methylene chloride, washed with water and dried to give BHPF (99.8 percent by weight of 4,4-isomer) . EXAMPLE 26 CONDENSATION OF PHENOL AND ACETONE TO PRODUCE 2.2-BTfi- - HYDROXYPHENYL) PROPANE A. FEED CONTAINING 6 percent BY WEIGHT OF ACETONE, PLUS WATER. SOLUBLE CATALYST: BATCH REACTION The reaction was carried out in a 2-L jacketed baffled resin pot, equipped with a condenser and nitrogen purge. Isothermal temperature control was provided by a fluid material, circulated through the reactor jacket. Stirring was provided by a stirrer, equipped with an impeller. To the reactor was charged 1200 g of feed, containing 90.0 percent by weight of phenol, 6.0 percent by weight of acetone, 1.8 percent by weight of water and 2.2 percent by weight of MPSA. The mixture was heated at 35°C. At the end of 2 hours' heating, crystallization occurred in the reaction mixture. The reaction was continued 1 hour more, at the end of which 80 percent of the acetone was reacted (as determined by HPLC) . The reaction mixture was removed from the reactor and filtered. The weight of recovered crystals was 17 percent, consisting of a 1:1 adduct of BPA:phenol (molar ratio) . The crystalline adduct was washed with phenol. The washed adduct contained 57.7 percent by weight of 4,4-bisphenol, 160 ppm of 2,4- bisphenol, 200 ppm of trisphenol, 2270 ppm of other trace bisphenolic impurities and 1170 ppm of MPSA, the balance being phenol. The mother liquor contained 8.44 percent by weight of 4,4-bisphenol, 0.26 percent by weight of 2,4- bisphenol, 0.13 percent by weight of trisphenol 0.62 percent by weight of other bisphenolic impurities, 0.81 percent by weight of acetone, 2.95 percent by weight of water and 2.78 percent by weight of MPSA, the balance being phenol. B___ REACTION USING RECYCLED MOTHER LIQUORS The mother liquor from (A) was charged to a rotary evaporator with make-up phenol (181 g) . The evaporator was heated at 50°C for 30 min, at the end of which the conversion of acetone was 90 percent. Pressure was reduced to 10 mm Hg absolute for 30 min, at the end of which the mixture contained 1.4 percent by weight of water. The acetone content was below the detection limit. The dried mother liquor was returned to the reactor, along with make-up phenol, acetone, water and MPSA to give a mixture containing 92.0 percent by weight of phenol, 4.0 percent by weight of acetone, 1.8 percent by weight of water and 2.2 percent by weight of MPSA. The total mass corresponded to (A) , minus the weight of samples removed. The mixture was stirred and heated at 35°C for 3 hr. Crystallization of BPA was observed after the initial 30 min of heating. At the end of 3 hours' heating, acetone conversion was 80 percent. The reaction mixture was processed as in (A) . Recycling of the mother liquors was repeated for 12 cycles. Results are given in Tables XIV and XV. These experiments demonstrate that catalyst and unreacted-materials can be recovered and recycled without adversely affecting the process and that results for successive runs were generally consistent and predictable. £ REACTION USING 10 percent BY WEIGHT OF ACETONE IN THE FEED WITH 3 percent BY WEIGHT OF WATER An experiment was done as in (A) , using 1200 g of feed, containing 85.5 percent by weight of phenol, 10.0 percent by weight of acetone, 3.0 percent by weight of water and 2.2 percent by weight of MPSA. The reaction was done at 25°C. Crystalline BPA was visible after 13 h at this temperature. At the end of 24 h, the conversion of acetone was 40 percent. Crystalline product, removed from the reaction mixture by filtration, constitutes 15 percent of the mixture. The crystals, a 1:1 adduct of BPA:phenol, were washed with phenol. The washed crystals contained 51.8 percent by weight of the 4,4-isomer, 60 ppm of 2,4-isomer, <20 ppm of trisphenol, 690 ppm of other trace bisphenols and 840 ppm of MPSA, the remainder being phenol. The mother liquors contained 6.73 percent by weight of 4,4-isomer, 0.15 percent by weight of 2,4-isomer, 0.,08 percent by weight of trisphenol, 0.76 percent by weight of other bisphenols, 5.71 percent by weight of acetone, 4.97 percent by weight of water and 2.66 percent by weight of MPSA, the remainder being phenol. A 15.00 g sample of 200-400 mesh chloromethylated polystyrene / 2 percent divinylbenzene co-polymer beads (approximately 4.3 mmol Cl/g resin, approximately 64.5 mmole Cl) known in the art as a Merrifield resin (commercially available from Fluka Chemie AG) was added to a round bottom glass flask (reactor) under a pad of plant nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl) . (3-Bromopropyl)benzene (102.7 g, 78.4 mL, 8.0 equivalents) was added to the dry resin beads. Dried (over 3 Angstrom molecular sieves) nitrobenzene (50 mL) was added, and the beads were slowly stirred at room temperature to allow for swelling of the beads. The reactor was cooled to 0°C in an ice water bath. A 20 mL sample of 1.0 M aluminum chloride in nitrobenzene commercially available from Aldrich Chemical Co. was slowly added via syringe to the cold polymer slurry with rapid stirring over approximately 10 minutes. The mixture turned dark red as soon as the aluminum chloride solution was added and exothermed to approximately 4°C within the first 15 minutes of reaction with HCl being evolved from the solution. After the addition of the AICI3/nitrobenzene solution was complete, the mixture was slowly stirred at 0°C for 2-3 hours, then was removed to room temperature and slowly stirred overnight. The mixture was slowly poured onto ice to quench the aluminum chloride. Then the beads were separated using a glass- fritted funnel with vacuum filtration. The beads were sequentially washed with water, acetone, dichloromethane, methanol, dilute aqueous hydrochloric acid, water and methanol, then were dried overnight in a vacuum oven at 70°C (dry mass 23.52 g) . R. Sulfonation The polymer beads from Example 27A (23.30 g, estimated 161.3 mmole of phenyl groups) were added to a glass reactor with addition funnel and NaOH scrubber attached. Dichloromethane (100 mL) was added to the flask and the beads were allowed to swell (rapid swelling was observed) . The slurry was cooled to 0°C in an ice water bath. Chlorosulfonic acid (37.6 g, 21.4 mL, 320 mmole, approximately 2.0 equivalents per equivalent phenyl groups) was slowly added dropwise over approximately 2 hours to the polymer slurry at 0°C. The mixture was allowed to slowly warm to room temperature overnight in the water bath. The mixture was slowly poured onto ice to quench the excess chlorosulfonic acid, then the beads were separated using a glass-fritted funnel with vacuum filtration. The beads were then washed extensively with water. Water was added to make a slurry, then solid sodium bicarbonate was slowly added in small portions over approximately 2 hours until no more bubbling was observed (all active acid sites neutralized) . The mixture was allowed to stand 3 days in the aqueous sodium bicarbonate solution (some additional bead swelling was observed over this time period) . The beads were washed with water and transferred to a glass reactor with 100 mL of water. The beads were then heated to 70-80°C over 2 hours to ensure hydrolysis of any residual sulfonyl chloride groups. C- Thiolation The aqueous polymer slurry from Example 27B was cooled to room temperature. Sodium bicarbonate was slowly added until the slurry was neutral (no bubbling observed) , then additional sodium bicarbonate (27.1 g, 323 mmol) was added to the aqueous bead slurry. Thiolacetic acid (24.6 g, 23.1 mL, 323 mmol) was added to an addition funnel. The reactor was evacuated and refilled with nitrogen several times to minimize the air content. The thiolacetic acid was slowly added over approximately 15-20 minutes to the aqueous bead slurry with rapid stirring. The addition rate was adjusted to control the effervescent evolution of carbon dioxide which was formed in the neutralization process. After the thiolacetic acid addition was complete, the mixture was heated to 70°C and was allowed to react overnight with minimal stirring. The mixture was then cooled to room temperature and the beads were collected by filtration using a fritted-glass funnel. The beads were washed extensively with water, then with dichloromethane, and then washed again with water. The beads were transferred back to the glass reactor, then concentrated (12 molar) hydrochloric acid (100 mL) was added. The mixture was heated with mild stirring to 50°C for 4-5 hours, then was cooled to room temperature. Deionized water (100 mL) was added and the beads were again collected by filtration using a fritted-glass funnel. The beads were washed with water, then were washed extensively (approximately 500 mL) with dilute (approximately 3 molar) aqueous hydrochloric acid. The beads were then washed again with deionized water and finally were washed with methanol to displace the water and shrink the polymer beads. The beads were dried overnight in a vacuum oven at 70 °C (dry mass 34.17 g) . The final polymer catalyst isdesignated herein as DPMSA- MER3C P. Preparation of Three-Carbon DPMSA Polymer From Merrifield Resin Beads Another mercaptosulfonic acid polymer was prepared using the procedure of steps A-C of Example 27, except using a chloromethylated polystyrene resin (2 percent divinylbenzene, 200-400 mesh, approximately 4.3 mmol Cl/g resin) , a Merrifield resin commercially available from Fluka Chemie AG as the polymeric support and (3- bromopropyl)benzene in the alkylation step of the reaction. The resulting polymer is identified herein as DPMSA-MER3C. E. Preparation of Three-Carbon DPMSA Polymer From Chloromethylated Gel-Resin Beads Another mercaptosulfonic acid polymer was prepared using the procedure of steps A-C of Example 27, except using a chloromethylated 1.5 percent crosslinked polystyrene gel- resin (-30+70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (3-bromopropyl)benzene in the alkylation step of the reaction. This polymer is identified herein as DPMSA-1.5X3C. F. Preparation of Two-Carbon DPMSA Polymer From Chloromethylated Gel-Resin Beads Another mercaptosulfonic acid polymer was prepared using the procedure of steps A-C of Example 27, except using a chloromethylated 1.5 percent crosslinked polystyrene gel- resin (-30+70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (2-bromoethyl)benzene in the alkylation step of the reaction. This polymer is identified herein as DPMSA-1.5X2C. S . Preparation of three Carbon DPMSA from 6 percent Crosslinked Macroporous Resin Another mercaptosulfonic acid polymer was using the procedure of steps A-C of Example 27, except using a chloromethylated 6 percent crosslinked macroporous polystyrene resin (approximately 30-70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (3- bromopropyl)benzene in the alkylation step of the reaction. This polymer is identified herein as DPMSA- 6/42-3C. H. Preparation of three Carbon DPMSA from 6.5 percent Crosslinked Gel Resin Another mercaptosulfonic acid polymer was using the procedure of steps A-C of Example 27, except using a chloromethylated 6.5 percent crosslinked uniform particle size polystyrene gel-resin (380 micron, approximately 4.3 mmol Cl/g resin) as the polymeric support and (3- bromopropyl)benzene in the alkylation step of the reaction. This polymer is identified herein as DPMSA- 6.5X3C. EXAMPLE 28 EVALUATION OF CATALYSTS IN CONTINUOUS PROCESSES A fixed bed downflow reactor, having a volume of 10-mL, was constructed from a vertical tube, filled with catalyst. External to the catalyst bed was a preheater area, packed with glass wool. Ancillary equipment included a pressure regulator, relief valve, pump and heater for the feed. The feed was heated by heating fluid, circulated through the feed pot, and was kept under a nitrogen pad. The feed was phenol (99.9 percent) and fluorenone (approximately 99 percent) in a 21:1 molar ratio. The heating fluid, heating tape and reactor were turned on. The selected catalyst was slurried in phenol at approximately 45°C. Catalyst-phenol mixture was pipetted into the reactor, at the bottom of which a plug of glass wool/glass beads was placed to prevent catalyst from leaving the reactor. The phenol:fluorenone was added to the feed pot at 55°C. The pressure was adjusted to approximately 0.34 bars. Phenol:fluorenone feed was introduced into the reactor and the composition of the effluent from the reactor was followed by HPLC. The following results were obtained: Table XVI PMBSA-Mer catalyst (Example 9C) at 50°C: productivity 1.4 g BHPF/g cat h conversion time (h) percent fluorenone conversion 0.33 99.7 28 100.0 53 100.0 69 99.7 89 99.9 113 100.0 137 99.8 144 99.6 162 99.6 selectivity 98 percent 4,4-BHPF PMRSA-XEBr (Example 9D. at 69°C. productivity 0.6 g BHPF/g cat h conversion time (h) percent fluorenone conversion 2 99.8 15 100.0 39 100.0 63 98.9 79 99.0 103 95.5 127 87.1 164 83.4 selectivity 98 percent 4, 4 -BHPF PMBSA-XECl (Example 9EΪ at 56°C: productivity 1.48 g BHPF/g cat h conversion time (h) percent fluorenone conversion 2 99.2 27 99.1 63 99.3 87 98.7 111 98.9 135 98.6 159 98.3 164 98.0 selectivity 98 percent 4,4-BHPF XEMSA-11C (Example 22D. at SOT- conversion time (h) percent fluorenone conversion 1 99.2 17 94.4 41 92.2 65 91.0 nPMSA-MER3C (Example 27D. at 50°C: selectivity 98 percent p,p-BHPF productivity 4 lb BHPF/ lb catalyst/hour = 4 kg/kg/h conversion time (h) percent fluorenone conversion 20 99.9 24 99.9 39 99.9 48 100.0 66.5 100.0 75.5 98.9 99.5 . 99.1 103 98.6 104 98.7 XEMSA-5C (Example 22) at 55T- selectivity 98 percent p,p-BHPF productivity 0.43 lb BHPF/lb catalyst/hour =0.43 kg/kg/h conversion time (h) percent fluorenone conversion 4 99.7 22 100.0 46 100.0 70 100.0 77 99.7 94 99.7 118 99.7 142 99.5 144 99.4 168 99.3 192 99.0 216 99.0 240 98.6 264 98.6 DPMSA-XE-.C (Example 27A-C. at 56°r * . selectivity 98 percent 4,4-BHPF conversion time (h) percent fluorenone conversion 30 98.0 48 95.1 72 94.7 96 92.3 123 87.3 144 86.1 170 83.8 240 77.1 These results show that PMBSA, XEMSA, and DPMSA catalysts of the invention can exhibit stability over time, thus, have very useful lifetimes. EXAMPLE 29 CONTINUOUS PROCESS FOR MAKING BHPF USING MERCAPTOPROPANESULFONIC ACID CATALYST The reactor comprised a three-staged continuous reactor (isothermal perfectly stirred type) . The reaction was run at 46°C at a 21:1 molar ratio of phenol :fluorenone (98 percent, Aldrich), the amount of MPSA being 0.05-0.07 equivalent of MPSA:mole of fluorenone. The composition of the products was followed by HPLC. The reaction was continued for 228 h, at the end of which fluorenone conversion was 99.95 percent (reactor 2) or 99.9 percent (reactor 1) and selectivity to 4,4-BHPF was 98.32 percent (reactor 2) or 95.2 percent (reactor 1) . EXAMPLE 30 EVALUATION OF CATALYST OF EXAMPLE 22D (XEMSA-5C) IN CONTINUOUS PROCESS FOR MAKING BISPHENOL A The reactor comprised a vertical upflow column of stainless steel tubing, packed with resin atop a screen and glass beads. The column was heated by a water jacket. The progress of the reaction was followed as above by HPLC. The following results were obtained: Table XVII Test 25% promoted XEMSA- 5C Dowex™ 50Wx4 Example 22D - = approximately % = percent EXAMPLE 31 PREPARATION OF BISPHENOL F Phenol and formaldehyde were reacted to produce bisphenol F. Similar results were obtained. Example 32 Alternate Preparation of a Representative r (Mercaptoalkyl) (Sulfo) -Phenylal yl! Sulfonated Polystyrene Catalyst (Designated DPMSAA- .25-1.5X2C) A Preparation of (2-Bromoethyl)benzyl Chloride (Al) In an extension of the procedure described by Selva, M; Trotta, F.; and Tundo, P. Synthesis , 1991, 1003-1004, (2-bromoethyl)benzylchloride was prepared by the following procedure: Concentrated sulfuric acid (132 mL) was slowly added to ice cold deionized water (66 mL) in a 1 L three-necked glass reactor fitted with a mechanical stirrer, reflux condenser, and temperature probe. The reactor containing the sulfuric acid solution was cooled in an ice bath, then (2-bromoethyl)benzene (92.5 g, 0.50 mole) was added followed by 50 percent tetrabutylammonium chloride in water (10 g of solution), paraformaldehyde (20.Og, 0.666 mole, 1.33 equivalents), and finally sodium chloride (80.0 g, 1.37 mole, 2.74 equivalents) . The slurry was stirred at approximately 1000 rpm (very vigorous) and heated to 80°C for 2.25 hours. The reaction was less than 50 percent complete as determined by gas chromatographic analysis. Additional paraformaldehyde (20.0 g, 0.666 mole, 1.33 equivalents) was added and the mixture was stirred (600-700 rpm) an additional 3.5 hours at 80°C. The reaction was approximately 50 percent complete as determined by gas chromatographic analysis. The mixture was allowed to cool and was transferred to a separatory funnel. The organic phase was separated and saved for further reaction. (A2) Alternatively, (2-Bromoethyl)benzene (92.5 g, 0.50 mole) , concentrated (12 molar) hydrochloric acid (125 mL, 1.5 mole HCl, 3 equivalents HCl), and paraformaldehyde (22.5 g, 0.75 mole, 1.5 equivalents) were added to a 1 L three-necked glass reactor fitted with a mechanical stirrer, addition funnel, and temperature probe. Concentrated sulfuric acid (111 mL, approximately 205 g, approximately 4 equivalents of sulfuric acid) was added to the addition funnel. A small portion (approximately 10-15 mL) of the sulfuric acid was added to the reaction mixture from the addition funnel and the slurry was heated to 80°C with stirring at aproximately 1000 rpm. After the reaction reaches 80°C, the remaining concentrated sulfuric acid was added dropwise over 3 hours. After an addition 1 hour reaction time, the reaction was less than 50 percent complete as determined by gas chromatographic analysis. The mixture was allowed to cool and was transferred to a separatory funnel. The organic phase was separated and saved for further reaction. The combined products from Example 32, parts Al and A2 containing unreacted (2-bromoethyl)benzene and chloromethylated (2-bromoethyl)benzene products (mixture of isomers) were further chloromethylated according to the procedure described in part Al. The reaction was performed using sufficient time and reagent (paraformaldehyde, sodium chloride, sulfuric acid) charges to completely consume the (2-bromoethyl)benzene starting material, giving a mixture of (2-bromoethyl)benzyl chloride isomers along with higher-boiling by-products. The mixture of (2-bromoethyl)benzyl chloride isomers was isolated by oil-pump vacuum bulb-to-bulb Kugelrohr distillation (up to 140-145°C) . The isolated product was a water-white oil which solidifies upon standing at room temperature. Gas chromatography analysis showed that unreacted (2-bromoethyl)benzene and the higher boiling by¬ products were essentially absent from the distilled (2- bromoethyl)benzyl chloride isomers product. R_ Alkylation Styrene/divinylbenzene co-polymer resin beads (10.00 g, - 30+70 mesh, 1.5 percent divinylbenzene, approximately 96.0 mmole styrene repeat units) were added to a round bottom glass flask (reactor) under a pad of nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl) . A solution of (2-bromoethyl)benzyl chloride (mixture of aromatic ring isomers, predominately para) (10.0 g, 0.238 equivalents based upon styrene repeating units) in 1,2- dichloroethane (25 mL) was added to the dry resin beads. The beads were allowed to swell for approximately 5-10 minutes, then additional 1,2-dichloroethane (35 mL) was added to the swollen beads. Anhydrous tin(IV) chloride (2.5 mL, approximately 5.57 g, approximately 21.4 mmol) was slowly added via syringe to the polymer slurry at room temperature over approximately 10 minutes with rapid stirring. The mixture turned light yellow when the tin(IV) chloride was added. The mixture was slowly warmed (in 5°C increments) to 40°C over approximately 30 minutes and was allowed to react at 40°C for 1 hour. At this time the light orange mixture was slowly warmed (in 5°C increments) to 60°C over approximately 1 hour 30 minutes and was allowed to react overnight at 60°C with slow stirring. After overnight reaction, the mixture was cooled to room temperature and was quenched by slowly adding methanol to the well-stirred polymer slurry. The beads were separated from the solution using a glass- fritted funnel with vacuum filtration. The beads were sequentially washed (three portions each) with dichloromethane, water, tetrahydrofuran, and methanol, then the beads were dried overnight in a vacuum oven at 80°C (dry mass 13.89 g) . Theoretical mass yield = 14.49 g. Alkylation yield (by mass uptake) = 87 percent. Approximate degree of polymer functionalization (by mass yield) = 0.21. C. Sul onation The polymer beads from Example 32B (13.89 g, estimated 116 mmole of phenyl groups) were added to a glass reactor with addition funnel and NaOH scrubber attached. Dichloromethane (75 mL) was added to the flask and the beads were allowed to swell (rapid swelling was observed) . The slurry was cooled to approximately 3-5 °C in an ice water bath. Chlorosulfonic acid (11.7 mL, approximately 20.5 g, approximately 176 mmol, approximately 1.5 equivalents per equivalent of phenyl groups) was slowly added dropwise over approximately 30 minutes to the cold polymer slurry with stirring. The mixture was allowed to react at approximately 3-5°C in an ice water bath for 1 hour. The mixture was removed from the ice bath and allowed to warm to room temperature over 2 hours 45 minutes. At this time, the polymer slurry was again cooled to 3-5°C in an ice water bath, and water was slowly added with rapid stirring to quench the excess chlorosulfonic acid. The beads were separated using a glass-fritted funnel with vacuum filtration. The beads were then washed extensively with water. Water was added to make a slurry, then solid sodium bicarbonate was slowly added in small portions with stirring until no more bubbling was observed (all active acid sites were neutralized) . The beads were washed with water and transferred back to the glass reactor with 100 mL of water. The beads were then heated to 60-70°C over 2 hours to ensure hydrolysis of any residual sulfonyl chloride groups. P. Thiolation The aqueous polymer slurry from Example 32C (estimated approximately 20 mmole Br) was cooled to room temperature. Sodium bicarbonate was slowly added until the slurry was neutral (no bubbling observed) , then additional sodium bicarbonate (5.30 g, 63.0 mmol, approximately 3 equivalents relative to estimated bromine content in beads) was added to the aqueous bead slurry. Thiolacetic acid (4.5 mL, approximately 4.8 g, approximately 63 mmol, approximately 3 equivalents relative to estimated bromine content in beads) was added to an addition funnel. The reactor was evacuated and refilled with nitrogen several times to minimize the air content. The thiolacetic acid was slowly added over approximately 10-15 minutes to the aqueous bead slurry at room temperature with rapid stirring. The thiolacetic acid addition rate was adjusted to control the effervescent evolution of carbon dioxide which was formed in the neutralization process. After the thiolacetic acid addition was complete, the mixture was heated to 70°C and was allowed to react overnight with minimal stirring. The mixture was then cooled to room temperature and the beads were collected by filtration using a fritted-glass funnel. The beads were washed extensively with water, then with dichloromethane (optional) , and then washed again with water. The beads were transferred back to the glass reactor, then concentrated (12 molar) hydrochloric acid (100 mL) was added. The mixture was heated with mild stirring to 50°C for 2-3 hours, then was cooled to room temperature. Deionized water (100 mL) was added and the beads were again collected by filtration using a fritted-glass funnel. The beads were washed with water, then were washed extensively (approximately 500 mL) with dilute (approximately 3 molar) aqueous hydrochloric acid. The beads were then washed again with deionized water and were transferred to a storage bottle without any additional drying. The final polymer catalyst had a titrated water- wet (water swollen) acid capacity of 0.80 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.25-1.5X2C E____ Preparation of DPMSAA Resin with 0.71 Equivalents Alkylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure described in steps B-D of Example 32, except using 0.71 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (2.0 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a 83 percent yield in the alkylation reaction and a degree of functionality of 0.59. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.75-1.5X2C. F. Preparation of DPMSAA Resin with 0.43 Equivalents Al ylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure described in steps B-D of Example 32, except using 0.43 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (2.0 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was was in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a 81 percent yield in the alkylation reaction and a degree of functionality of 0.35. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.85 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.45-1.5X2C. ≤ . Preparation of DPMSAA with 0.095 Equivalents Alkylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure described in steps B-D of Example 32, except using 0.095 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a 99 percent yield in the alkylation reaction and a degree of functionality of 0.094. The final polymer catalyst had a titrated water- wet (water swollen) acid capacity of 0.80 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.10-1.5X2C. IL_ Preparation of DPMSAA with 0.42 Equivalents of (2- BromoethyDbenzylchloride Alkylation and 0.30 Equival n .-*-. of Benzyl Chloride Alkylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure described in steps B-D of Example 32, except using 0.42 equivalents of (2- bromoethyl)benzyl chloride and 0.30 equivalents of benzyl chloride in the alkylation reaction. Chlorosulfonic acid (2.0 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.45/0.30-1.5X2C. I . Preparation of DPMSAA Resin having 0.423 Equivalents Alkylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure of steps B-D of Example 32, except using 0.423 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction and directly carrying the polymer slurry obtained from the alkylation reaction directly on to the sulfonation reaction without any quenching, isolation, or washing steps after the alkylation reaction. Chlorosulfonic acid (1.25 equivalents relative to the total equivalents of phenyl groups present in all reactants) was added directly to the polymer slurry after the alkylation reaction was complete. Workup and subsequent isolation of the product after sulfonation was as in Example 32, except that more extensive washing was required to remove soluble reaction by-products from the polymer slurry. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the estimated maximum amount of bromine present in the polymer) were used in the thiolation reaction. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.78 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.45NW-1.5X2C. J. Preparation of DPMSAA Resin with 0.238 Equivalents Alkylation Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using a variation of the procedure described in Example 32. The alkylation and sulfonation reactions were performed in one step utilizing chlorosulfonic acid as the alkylation catalyst and sulfonation reagent . Styrene/divinylbenzene co-polymer resin beads (10.00 g, - 30+70 mesh, 1.5 percent divinylbenzene, approximately 96.0 mmol styrene repeat units) were added to a round bottom glass flask (reactor) under a pad of plant nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl) . A solution of (2-bromoethyl)benzyl chloride (mixture of aromatic ring isomers, predominately para) (5.32 g, 0.238 equivalents based upon styrene repeat units) in 1,2- dichloroethane (25 mL) was added to the dry resin beads. The beads were allowed to swell for approximately 5-10 minutes, then additional 1,2-dichloroethane (35 mL) was added to the swollen beads. The slurry was cooled 2-3°C in an ice bath, then chlorosulfonic acid (12.0 mL, approximately 21.0 g, 1.5 equivalents based upon total equivalents of phenyl groups in the mixture) was added slowly dropwise over approximately 1 hour 45 minutes. The mixture was allowed to stir an additional 1 hour at 3-4°C, then was removed to room temperature and allowed to react an additional 1.5 hours. The mixture was then cooled in an ice water bath and water was slowly added to quench the excess chlorosulfonic acid. Thereafter the beads were isolated according to the procedure described in part C of Example 32. Likewise, the thiolation reaction was as in part D of Example 32 using thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the estimated maximum amount of bromine in the polymer) . The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-2S-0.25-1.5X2C. K. Preparation of DPMSAA Resin Having 6.5 percent Crosslinkinα Another mercaptosulfonic acid polymer was prepared from 6.5 percent crosslinked styrene/divinylbenzene co-polymer beads (380 micron uniform particle size spheres) using the procedure described in steps B-D of Example 32, except using 0.427 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a 57 percent yield in the alkylation reaction and a degree of functionality of 0.24. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 1.75 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.45-6.5X2C. L. Preparation of DPMSAA Resin with 0.25 Equivalents Alkylation and Having 1.8 percent Crossl nking Another mercaptosulfonic acid polymer was prepared from 1.8 percent crosslinked styrene/divinylbenzene co-polymer beads (-25+40 mesh) using the procedure described in steps B-D of Example 32, except using 0.25 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to an 86 percent yield in the alkylation reaction and a degree of functionality of 0.22. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.85 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.25-1.8X2C. M. Preparation of DPMSAA Resin with 0.10 Equivalents Alkylation and Having 1.8 percent Crosslinking Another mercaptosulfonic acid polymer was prepared from 1.8 percent crosslinked styrene/divinylbenzene co-polymer beads (-25+40 mesh) using the procedure described in steps B-D of Example 32, except using 0.10 equivalents of (2- bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.81 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-0.10-1.8X2C. N- Preparation of 1.5 percent Crosslinked DPMSAA Resin with 0.10 Equivalents Alkylation and Using Sodium Hydrosul ide in the Thiolation Reaction Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using a variation of the procedure described in steps B-D of Example 32, except using 0.10 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction and sodium hydrosulfide in the thiolation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Sodium hydrosulfide (6.4 equivalents relative to the calculated amount of bromine in the polymer) was used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a degree of functionality of 0.10. The final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.82 milliequivalent/mL catalyst. The final polymer catalyst is designated herein as DPMSAA-AT-0.10-1.5X2C. O. Preparation of DPMSAA Resin with 0.25 Equivalents Alkylati n and Having 4 percent Crosslinking Another mercaptosulfonic acid polymer was prepared from 4 percent crosslinked styrene/divinylbenzene co-polymer beads (360 micron uniform particle size spheres) using the procedure described in steps B-D of Example 32, except using 0.25 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to a 73 percent yield in the alkylation reaction and a degree of functionality of 0.18. The final polymer catalyst is designated herein as DPMSAA-0.25-4X2C. P. Preparation of DPMSAA Resin w th 0.10 Equivalents Alkylation and Having 4 percent Crossl inking Another mercaptosulfonic acid polymer was prepared from 4 percent crosslinked styrene/divinylbenzene co-polymer beads (360 micron uniform particle size spheres) using the procedure described in steps B-D of Example 32, except using 0.10 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction. The mass yield of polymer obtained from the alkylation reaction corresponded to an 74 percent yield in the alkylation reaction and a degree of functionality of 0.074. The final polymer catalyst is designated herein as DPMSAA-0.10-4X2C. Example 33 Evaluation of Catalysts in a Continuous Process A three-stage up-flow reactor was constructed from three vertical stainless steel tubes with sampling ports between each section. Each reactor stage was water jacketed for temperature control with all connecting lines heat-traced to prevent reactor line plugging. Likewise the 2L reactor feed tank was jacketed so that precise control of the reactor feed could be obtained. From the feed tank, feed flowed through an electrically heat-traced section of tubing for control of feed input temperature. Each reactor section was packed with 10-20 mL of water-wet catalyst. The reactor feed consisted of a solution of 4 weight percent acetone in phenol. The acetone:phenol mixture was precisely metered into the temperature controlled reactor system at a defined combination of flow rate (1.0 mL/min to 2.0 mL/min) and reactor temperature (55°C to 65°C) . Upon start-up of each new loading of catalyst, the feed passed through the catalyst for at least 12 hours before measurements were recorded to remove water from the catalyst. Product composition of the reactor effluent from each of the three stages was analyzed by HPLC while gas chromatography was used to analyze for acetone and water. The results obtained from tests of the catalysts at various times of reaction (reactor residence times) are in Table XIX. Productivity is expressed in terms of pounds of bisphenol A produced per hour per cubic foot (2.8 x 10~ 2 cubic meter) of water-swollen catalyst charged into the reactor. (NOTE: Unless otherwise noted, all of the catalyst results were obtained at 55°C.) * is percent conv. is conversion prod, is product Bisphenol A op/pp is the ratio of ortho. para bisphenol tr* para, parabisphenol tris is higher oligomeric adduct derived from the reaction of 2 acetone molecules with 3 phenol molecules cyclics are bv-products having dianins. spirobiindanols. and dihydroindanols tot, imp, is total impurities including ortho. para bishenol A. tris. cyclics as well as other unidentified product peaks. The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples. From the foregoing description, one skilled in the ' art can easily ascertain the essential characteristics of this invention and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

Claims: Claims: 1. A process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in at least one position, comprising reacting the aldehyde or ketone starting material with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material; provided that the soluble mercaptosulfonic acid compound is characterized by the formula (HS) a -θ-(S0 3 H) b wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b are independently selected from integers from 1 to about 20; and the insoluble mercaptosulfonic acid comprises a catalytically-active species represented by the formula (HS) a -θ'-(S0 3 H) b (a) t in which θ' is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to about 20; L is an optional linking group and - is a bond, which catalytically-active species is attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by the unit formula (HS) a (S0 3 H) b \ / - [ θ" - L']- - (b) wherein θ" is an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to about 20; L' is an optional linking group and - is a bond. 2. The process of claim 1, wherein the mercaptosulfonic acid compound is soluble in the reaction mixture and is characterized by the formula (HS) a -θ-(S0 3 H) b wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b are independently selected from integers from 1 to about 4. 3. The process of claim 2, wherein the mercaptosulfonic acid compound is generated in the reaction mixture by reaction between an alkali metal salt of a mercaptosulfonic acid and a mineral acid, reaction between a mercaptosulfonate ester and an alkali metal hydroxide, or reaction between a mercaptosulfonyl halide and a mineral acid. 4. The process of claim 2, wherein the mercaptosulfonic acid compound is a mercaptoalkanesulfonic acid of up to about 20 atoms between the mercapto and sulfonic acid groups. 5. The process of claim 2, wherein the mercaptosulfonic acid compound is 3- mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanesulfonic acid, or mixture thereof. 6. The process of claim 1, wherein the molar ratio of phenol to aldehyde or ketone is from about 0.5:1 to about 50:1, the process is carried out at a temperature from about 15°C to about 60°C, and the reaction mixture contains from about 0.01 to about 2.0 equivalent of mercaptosulfonic acid per mole of aldehyde or ketone. 7. The process of claim 1, carried out with removal of water from the reaction mixture. 8. The process of claim 1, wherein water is added to the reaction mixture to depress the freezing point of the phenol. 9. The process of claim 1, wherein the ketone is fluorenone, the phenol is unsubstituted and the product is 9, 9-bis- (4-hydroxyphenyl) fluorene, the phenol is unsubstituted and the product is 2,2-bis-(4- hydroxyphenyl)propane, or the ketone is 4- hydroxyacetophenone, the phenol is unsubstituted and the product is 1, 1, 1-tris- (4-hydroxyphenyl) ethane. 10. The process of claim 9, wherein a resulting crude product is washed with water to remove (HS) a -θ- (S0 3 H) b ; the resulting acid-free mixture is distilled to remove phenol and water until the phenol : 9, 9-bis- (4- hydroxyphenyl) fluorene weight ratio is less than about 2:1; the resulting mixture is taken up in hot methylene chloride and the resulting solution is cooled to produce crystalline 9, 9-bis- (4-hydroxyphenyl) fluorene. 11. The process of claim 9, carried out in the presence of a diluent which forms an adduct with 2,2-bis- (4-hydroxy-phenyl)propane under conditions such that 2,2- bis- (4-hydroxy-phenyl)propane crystallizes in the reaction mixture. 12. The process of claim 2, wherein the ketone is fluorenone, the phenol is unsubstituted and the product is 9, 9-bis- (4-hydroxyphenyl) fluorene; the molar ratio of phenol to fluorenone is from about 8:1 to about 25:1; the reaction mixture contains from about 0.05 to about 0.2 equivalent of mercaptosulfonic acid per mole of fluorenone; the mercaptosulfonic acid compound is 3- mercaptopropanesulfonic acid or 4-mercaptobutanesulfonic acid and the process is carried out at a temperature from about 45°C to about 60°C. 13. The process of claim 2, wherein the ketone is acetone, the phenol is unsubstituted and the product is 2,2-bis- (4-hydroxyphenyl)propane; the molar ratio of phenol to acetone is from about 6:1 to about 15:1; the reaction mixture contains from about 0.10 to about 0.50 equivalent of mercaptosulfonic acid per mole of acetone; the mercaptosulfonic acid compound is 3- mercaptopropanesulfonic acid or 4-mercaptobutanesulfonic acid and the process is carried out at a temperature from about 15°C to about 60°C. 14. The process of claim 2 , wherein crude product, resulting from the condensation, is extracted with water to remove (HS) a -θ- (S0 3 H) b from the product, extracted with an aqueous solution of an alkali metal hydroxide, carbonate or bicarbonate to remove (HS) a -θ- (S0 3 H) b from the product, or is treated with an anion-exchange resin to remove (HS) a -θ- (S0 3 H) b from the product. 15. The process of claim 2, comprising a process for making a bisphenol by the step of contacting an aldehyde or a ketone with excess phenolic compound in the presence of a catalytic amount of mercaptosulfonic acid catalyst, which is soluble in the reaction mixture, at a temperature' selected such that a bisphenol is formed and crystallizes in the reaction mixture. 16. The process of claim 15, wherein the ketone is acetone, the phenolic compound is phenol, and the bisphenol is bisphenol A, the temperature of the reaction is between about 0°C and about 50°C, and the catalyst is represented by the formula (HS) -θ- (S0 3 H) wherein θ is an alkylene, cycloalkylene or arylene moiety having from 2 to about 10 carbon atoms. 17. The process of claim 1, wherein the mercaptosulfonic acid is an insoluble material comprising a catalytically-active species represented by the formula (HS) a -θ'-(S0 3 H) b (a) t in which θ' is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to 20; L is an optional linking group and -is a bond, which catalytically-active species is attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by the unit formula (HS). (S0 3 H) b \ / - [ θ" - L'] - ' (b) wherein θ" is an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to 5; L' is an optional linking group and -is a bond, and the catalytically-active species is attached to the backbone of a polymer from at least one ethylenic monomer, or is incorporated in a polystyrene resin. 18. The process of claim 17, including the further steps of separating the catalytically-active material from the mixture; washing the catalytically-active material with a mixture of phenol and aldehyde or ketone and recycling the thus-washed material to the process. 19. The process of claim 17, wherein the polystyrene resin includes unit structures represented by the formula CRSO 3 H CnH2n CHR SH wherein B is a bridging group, R and R l are independently selected from H, alkyl and aryl, -C n H 2n - is straight or branched chain alkylene and n is an integer from 0 to 20; or the polystyrene resin includes unit structures represented by the formula: 20. The process of claim 1, including a further step of isomerizing a crude product in the presence of a mercaptosulfonic acid compound to increase the amount of 4,4-isomer in the mixture. 21. The process of claim 1, carried out in the presence of diphenylmethane as a diluent . 22. A process to make a bisphenol, comprising the step of contacting an aldehyde or a ketone with excess phenolic compound in the presence of a catalystic amount of a mercaptosulfonic acid catalyst, which is soluble in the reaction mixture, at a temperature selected such that a bisphenol is formed and crystallizes in the reaction mixture, wherein the ketone is actone, the phenolic compound is phenol, and the bisphenol is bisphenol A. 23. The process of claim 22 wherein the temperature of the reaction is between about 0°C and 50°C and the catalyst is represented by the formula: (HS).-Θ- (S0 3 H) b wherein θ is an alkylene, cycloaliphatic, arylene, alkylene-arylene, alkylene-cycloaliphatic, alkylene-aryl, heterocyclic, or alkylene-heterocyclic moiety, and a and b are each independently integers averaging from 1 to 4, and when θ is an alkylene moiety it has from 2 to 6 carbon atoms. 24. The process of claim 23 wherein the catalyst is selected such that at least 99 mole percent of the bisphenol A that crystallizes during the reaction is p,p'- bisphenol A. 25. A catalytically-active material comprising an insoluble organic or inorganic support in which is incorporated a mercaptosulfonic acid residue represented by the formula (HS) a -θ'-(S0 3 H) b t in which θ* is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to 20; L is an optional linking group and - is a bond, which catalytically-active species is attached by the bond - to the insoluble organic or inorganic support. 26. The catalytically-active material of claim 25, comprising a polystyrene resin including unit structures represented by the formula: CRS0 3 H CnH 2 n CHR SH wherein B is a bridging group, R and R 1 are independently selected from H, alkyl or aryl, -C n H 2n - is straight or branched chain alkylene and n is an integer from 0 to 20. 27. The catalytically-active material of claim 26, wherein B is CH 2 and -C n H 2n - is -CH 2 CH 2 - or -CH 2 - . 28. The catalytically-active material of claim 25, comprising a polystyrene resin including unit structures represented by the formula C,,H2 CH(R ) SH wherein R, R 1 , R 2 and R 3 are independently selected from H, alkyl or aryl and m is 0 to 10. 29. The catalytically-active material of claim 28, wherein R, R 1 , R 2 and R 3 each are H and m is 0, characterized by containing unit structures of the formula CHCH 3 SO3H CH2SH 30. The catalytically-active material of claim 28, wherein each of R, R 1 and R 3 is H, R 2 is methyl and is 2, characterized by the unit formula: SH 31. The catalytically active material of Claim 25 having a formula wherein n is an integer of from 0 to 10. 32. The catalytically-active material of Claim 25, wherein b is 2 or 3. 33. A process for making a catalytically-active material of Claim 26, comprising (a) reacting a haloalkylstyrene polymer with a lithiated sultone, (b) treating a resulting sultone-functionalized polymer with a reactive thiolate and (c) acidifying the resulting intermediate to produce a polymer containing (mercaptosulfoalkyl) styrene units. 34. The process of claim 33, wherein the haloalkyl- styrene polymer is a chloromethylated styrene/divinylbenzene polymer, the sultone is 1,4- butanesultone or 1,3-propanesultone and the resulting polymer contains (ε-mercapto-β-sulfopentyl) styrene or (δ- mercapto-β-sulfobutyl) styrene units. 35. A process for making a catalytically-active material of claim 28, comprising the steps of: (b) sulfonating a haloalkylpolystyrene to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to a sodium or potassium sulfonate function (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo functional group with a reactive thiolate to produce a corresponding mercapto functional group or precursor thereof; (e) optionally hydrolyzing the thus-thiolated intermediate with acid or base when the thiolated group so requires; and (f) optionally, acidifying (if so required) to produce the sulfonic acid function. 36. The process of Claim 35 wherein steps (b) - (f) are preceded by a step: (a) alkylating polystyrene with an alkenyl halide of the formula R(R 1 ) C=C(R 2 ) C m H 2m CH(R 3 )X, wherein each of R, R 1 , R 2 or R 3 is independently selected from H, alkyl or aryl; X is F, Cl, Br or I and is 0-10 to produce a haloalkyl polystyrene intermediate. 37. The process of Claim 36, wherein the alkenyl halide is allyl bromide, 5-bromo-1-pentene or 11-bromo-l- undecene. 38. The process of Claim 35 wherein steps (b) - (f) are preceded by a step: (a) alkylating a polystyrene resin with a halomethyl haloalkylarylene compound to produce an intermediate having [ (haloalkyl)phenylalkyl] styrene units, wherein the halomethyl haloalkylarylene compound is selected from chlorobenzylhalide, (chloromethyl)benzylhalide, (2-chloroethyl)benzylhalide, (3-chloropropyl)benzylhalide, (4-chlorobutyl)benzylhalide or corresponding fluoro, bromo or iodo analogs where the halide is selected from chlorine, bromine or iodine, particularly bromobenzylchloride, (bromomethyl)benzylchloride, (2-bromoethyl)benzylchloride, (3-bromopropyl) benzylchloride or (4-bromobutyl)benzylchloride. 39. The process of Claim 35 wherein steps (b) - (f) are preceded by a step: (a) alkylating a haloalkylated polystyrene with a haloalkylarylene compound to produce an intermediate having [ (haloalkyl)phenylalkyl] styrene units, wherein the haloalkylated polystyrene compound is selected from chlorobenzene, (chloromethyl)benzene, (2-chloroethyl)benzene, (3-chloropropyl)benzene, (4-chlorobutyl)benzene or corresponding fluoro, bromo or iodo analogs, particularly bromobenzene, (bromomethyl)benzene, (2-bromoethyl)benzene, (3- bromopropyl)benzene or (4-bromobutyl)benzene or a mixture thereof .

Inventors: BREWSTER STEVEN L, TASSET EMMETT L, WALTERS MARLIN E, WEHMEYER RICHARD M, BREWSTER, STEVEN, L., TASSET, EMMETT, L., WALTERS, MARLIN, E., WEHMEYER, RICHARD, M.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1995
Main classification: C07C37
IPC codes: B01J31, C07C37