Process for the preparation of bisphenols

Abstract: Triaromatic bisphenols are prepared by reacting a phenolic compound with at least one halo-compound selected from aromatic compounds having an (α,α-dihalo)alkyl or (α-halo)alk-1-enyl substituent with at least one β-hydrogen atom in said alkyl or alkenyl moiety, a trihalomethyl substituent or a dihalocyanomethyl substituent. Preferably, said halo-compound is 1,1-dichloroethylbenzene, 1-chlorostyrene, or mixtures thereof. The reaction may be conducted in the presence or absence of a solvent; an excess of the phenolic compound can serve as the solvent. The product is conveniently recovered by removing the by-product HCl, excess phenolic compound, excess solvent and cooling. Yields of greater than 90 percent of theoretical and a large proportion of para isomer can be obtained. Tris-(1,1,1-(4-hydroxyaromatic) toluenes are believed to be novel compounds.

Description: This invention relates to preparation of bisphenols, particularly bisphenols having a carbon atom having bonded thereto an aliphatic group and at least three aromatic groups, at least two of which aromatic groups each have at least one phenolic group hereinafter referred to as triaromatic bisphenols. Bisphenols are the building block molecules for such materials as polycarbonates, epoxy resins, polysulfones, polyarylates and the like. Bisphenols in which the phenolic rings are joined together through a single bridging carbon are usually manufactured by condensing two moles of phenol with an aldehyde or a ketone in the presence of an acid catalyst. Bisphenol A is the most commonly used bisphenol and is made from the reaction of acetone with phenol. Because it must be performed under mild temperature conditions (50-70°C) to minimize the formation of undesirable coproducts, it is a slow reaction. Other bisphenols are employed to impart specific properties to the above resins. Some of these properties are, for example, toughness, strength, better thermal properties and solvent resistance. Bisphenol AP, the bisphenol of phenol and acetophenone (bis-1,1-(4-hydroxyphenyl)-1-phenylethane), is known to improve the thermal properties of polycarbonates, polyarylates and epoxy resins over similar materials made from bisphenol A. The condensation of phenol with acetophenone, however, is very slow. Even with zinc chloride as a catalyst, the reaction requires two days to complete (US-A-4,467,122). Then an extended work-up must be performed to remove as much residual zinc salts as possible. With HCl as the catalyst, the reaction requires 10-14 days. These process limitations, along with the lack of commercially significant quantities of acetophenone, have hindered the development of useful applications for Bisphenol AP. A more facile process should allow wider use of this valuable monomer. In order to achieve the high molecular weights required to produce the desired thermal and mechanical properties, the bisphenol starting materials for such thermoplastics as polycarbonates and polyarylates preferably have the constituent phenol groups substituted in the para position in greater than 98 percent selectivity. Although most of the ortho-substituted material can be separated by crystallization, it is most desirable for good process economics to minimize the product containing any ortho isomer. In one reference, [ J. American Chemical Society , 76, 4547(1954)], 1-chloroethylbenzene is reported to react with phenol to give a mixture of isomers of bis-1,1-(hydroxyphenyl)-1-phenylethane having the hydroxy group of the phenyl group in the ortho and para position in a mole ratio of 55 ortho to 45 para position. US-A-4,048,200 discloses a process for preparing 1,1,2-tris-(2/4-hydroxyphenyl)-1-phenylethanes by reacting an ω-haloacetophone with a phenol. It acknowledges as prior art the preparation of 2,2-bis-(4-hydroxyphenyl)-propane (Bisphenol A) by reaction of acetone with phenol and the (difficult) preparation of 1,2,2-tris-(4-hydroxyphenyl) propane by reaction of chloroacetic acid with phenol. It is stated that if a methyl group of acetone is replaced by a phenyl group, only quite low yields can be obtained even after very long reaction times and that if both methyl groups of acetone are replaced by phenyl groups virtually no reaction takes place with phenol. It would be desirable to prepare triaromatic bisphenols more quickly than is typical for condensations of acetophenone with phenols and to prepare them such that there is a high selectivity for the para isomer. Bishydroxyphenyl compounds, including triaromatic bisphenols, are preferably in the para isomer form (having the hydroxy group on the phenyl ring para to the attachment of the phenyl ring to the carbon atom to which the other phenyl group(s) are attached) because such isomers result in high polymers with desirable properties of high molecular weight, impact strength, modulus and the like. According to the present invention, bisphenols are made by reacting a halo-compound which is (1) a trihalotoluene, (2) a dihalocyanotoluene, (3) an aromatic dihalo-compound having at least one aliphatic substituent having two alpha-halogen substituents and at least one beta hydrogen atom, (4) a corresponding halo-styrene or (5) mixtures thereof with a phenolic compound. At least two moles of the phenolic compound per mole of halo-compound are preferably employed. The reaction may be conducted with or without a solvent. The bisphenol is conveniently recovered by removing by-product HCl, excess phenolic compound and solvent (if any) and cooling to obtain the product. Alternatively, a crystallization solvent is used. In contrast with conventional technology, the new method is rapid and uses a simple purification to give the desired product. For instance, yields of bis-1,1-(4-hydroxy-phenyl)-1-phenylethane (Bisphenol AP) of up to 95 percent of theoretical can be obtained using this process. The reaction is broadly applicable with other aromatic hydroxy compounds such as naphthols and substituted phenols which can be reacted with the halo-compounds in place of phenol to prepare analogous bis-hydroxyaromatic derivatives. There is advantageously high selectivity for the para isomers. For instance, we have now discovered that under mild conditions, the reaction of phenol with 1,1-dichloroethylbenzene (DCEB) will produce bisphenol AP rapidly with excellent selectivity to the p,p' isomer, preferably with greater than 94 percent selectivity. This selectivity is unexpected in view of the known art. The process of the invention is represented by the reaction: wherein each R' is independently H or an aliphatic group; each R, or R'' is independently an inert substituent or an aliphatic or aromatic group wherein two or more R's and/or 2 or more R'''s are optionally joined to form cycloaliphatic or aromatic groups; R''' is CN or (R'')p-phenyl-OH in the case of the -CX₂Z starting material, -CHR'₂ in the case of the dihalo starting material or -CH₂R' in the case of the halostyrene starting material; X is a halogen, either chlorine or bromine, preferably chlorine; Z is a chlorine, bromine or a cyano group (CN); y is an integer of from 0 to 5, preferably from 0 to 2, more preferably from 0 to 1; p is an integer of from 0 to 4, preferably from 0 to 2, most preferably from 0 to 1. When R' is an aliphatic group, each R' preferably has from 1 to 15 carbon atoms, more preferably from 1 to 5 carbon atoms. Each aliphatic R, R' or R'' is unsubstituted or optionally inertly substituted. By "inert substituent" or "inertly substituted" it is meant that the substituent is one which does not undesirably interfere with the reaction of the aromatic halo-compound with a phenolic compound. Compounds wherein R''' is p-phenyl-OH are referred to herein as 1,1,1-tris(4-hydroxyphenyl)toluenes and are new compounds useful in making polymers. In the illustrated reaction sequence, the compounds having X substituents are those referred to herein as halo-compounds. The halo-compounds include dihalo alkyl aromatic compounds having an aliphatic substituent, said substituent having two alpha-halogen atoms (attached to an alpha carbon atom which is attached to an aromatic ring) and at least one beta hydrogen atom (attached to a beta carbon atom which is attached to the alpha carbon atom having the halogen atoms), optionally inertly substituted trihalotoluenes and cyanodihalotoluenes, and halo-styrene compounds corresponding to the dihalo alkyl aromatic compounds in structure except that one halogen atom and the beta hydrogen atom are eliminated and a double bond is between the alpha and beta carbon atoms. Either type of halo-compound is suitable for use in the practice of the invention. Suitable halo-compounds include 1-chlorostyrene; 1,1-dichloroethylbenzene (DCEB); 1-bromostyrene; 1,1-dibromoethylbenzene; 1,1-dichloro-n-hexylbenzene; 1,1,1-trichlorotoluene; 1,1,1-tribromotoluene; o-methyl-1,1,1-trichlorotoluene; 1-cyano-1,1-dichlorotoluene; m-ethyl-1,1,1-trichlorotoluene and mixtures thereof. Preferred compounds are 1-chlorostyrene, 1,1-dichloroethylbenzene and mixtures thereof. Such compounds wherein all the halogen atoms are chlorine are referred to herein as chloro-compounds. The process of the present invention can be illustrated by the process for making bis-1,1-(4-hydroxyphenyl)-1-phenylethane (Bisphenol AP) by contacting (a) 1,1-dichloroethylbenzene or 1-chlorostyrene or a mixture thereof, with (b) phenol, wherein the phenol is preferably present in an amount equivalent to at least a two molar multiple of the amount of (a) present. Reactants are preferably in liquid form. For instance, the halo-compound can be employed as a neat liquid and the phenol can be in its molten form or either one or both reactants can be dissolved in an inert solvent prior to contacting. After the reaction is desirably complete, the product bisphenol is recovered. For instance, the reaction mixture can be cooled to effect crystallization of the product bisphenol. Any method of recovery within the skill in the art is suitable. An alternative method of recovering the product is to remove the unreacted phenolic compound, the HCl produced in the reaction and solvent (if any) prior to cooling to effect the crystallization of the bisphenol. Yet another way of recovering the product is to remove most of the unreacted phenolic compound, then to add a solvent and cool to effect the crystallization of the bisphenol. Although the reaction is autocatalytic because the HCl produced by the reaction is an effective catalyst, any strong acid catalyst, advantageously HCl or any other hydrogen halide, may be added to the phenol as a catalyst for the reaction, preferably before the addition of the halo-compound because addition of the acid catalyst is more useful before the concentration of HCl produced in the reaction has reached a desired catalytic concentration. It is advantageous to conduct the reaction under a pressure greater than atmospheric by the use of a hydrogen halide, e.g. hydrogen chloride. The pressure of the hydrogen halide may vary from 1 to 100 atmospheres (0.1 - 10 MPa), preferably from 1 to 10 atmospheres (0.1 - 1 MPa). Triaromatic bisphenols (analogous to Bisphenol AP), can be prepared from aromatic hydroxyl compounds (any phenolic or thiophenolic compound which reacts with the halo-compound) such as naphthols and hydroxybiphenyl substituted phenols by reacting them with the halo-compounds. Thus, for example, naphthols, hydroxybiphenyls, alkylphenols, dialkylphenols thiophenols, nitrophenols and halophenols can be employed in place of the phenol reactant in the process. Specific hydroxyaromatic compounds useful in the reaction include o- and m-cresols, 2,6-dimethyl-phenol, nonylphenol, o- and m-chlorophenols, 2-napthol, 1-naphthol, ethylphenol, 2-methylthiolphenol, resorcinol, 2-nitrophenol, 3-nitrophenol and 2-chloro-thiophenol. Preferred compounds include alkyl phenolic having alkyl groups of from 0 to 5 carbon atoms and phenol; more preferred is phenol. Any molar ratio of phenolic compound to halo-compound which results in formation of the bisphenol is suitable but at least a stoichiometric molar ratio of at least two moles of phenolic compound to halo-compound is preferred, more preferably an excess of the stiochiometric amount of phenolic compound is used. Preferred mole ratios of phenolic compound to halo-compound are from 2:1 to 40:1, with 5:1 to 25:1 more preferred and from 5:1 to 15:1 most preferred. These molar ratios are preferred because they increase result in greater yields of bisphenol products and decrease yields of polymeric products formed by reaction of a halo-compound with the reaction product of one mole of chloro-compound with one mole of phenolic compound. Use of a large excess of phenolic compound e.g. greater than 25:1 is generally less preferred because it is wasteful of phenolic compounds or requires voluminous recycle. The reaction temperature is preferably from -20°C to +100°C, more preferably from 20° to 50°C most preferably room temperature. Temperatures above the preferred range can promote undesirable reactions, while those below the range make it difficult to maintain the reaction mass in molten condition (if no solvent is used) or will unduly slow the rate of reaction. Lower temperatures are, however, suitable when a solvent is used, but slower reaction rates are generally observed. Reaction solvents may include any solvent for the reactants which does not react undesirably with either the reactants or the products under reaction conditions. Preferred solvents include chlorinated aliphatic compounds, e.g. chloroform, carbon tetrachloride, trichloroethylene and the like; aromatic hydrocarbons, e.g. benzene, ethylbenzene and toluene; aromatic ethers such as phenyl ether; and halogenated aromatics such as chlorobenzene. Excess phenolic compound can also serve as a solvent for the reaction. Other useful solvents include tetrahydrofuran, acetic acid and nitriles such as acetonitrile. Trihalotoluenes and dihalocyanotoluenes are commercially available and can be prepared by means within the skill in the art. The aromatic dihalo-compounds having at least two aliphatic halogen atoms and at least one beta hydrogen atom, for instance 1,1-dichloroethylbenzene can be made by the chlorination of corresponding halohydrocarbons, for instance 1-chloroethylbenzene, with molecular halogen using a phosphorus halide catalyst, e.g. PCl₃ or PCl₅, in the presence of light or other initiator (see GB-A-1,563,164). A new and better method of making dihalo-compounds such as 1,1-dichloroethylbenzene is by reacting organic or inorganic hypochlorites with ethylbenzene to obtain good selectivity to 1,1-dichloroethylbenzene. A reactive hypohalite compound is reacted with an alkyl aromatic compound having at least one aliphatic substituent and which contains at least two alpha-hydrogens and in which each aliphatic substituent has at least one beta-hydrogen in the presence of a free radical generating medium. Useful hypohalites include alkali metal hypohalites used with phase transfer catalyst and t-alkyl hypohalites such as t-butyl hypochlorite. At least 2 moles of hypohalite is used for each mole of alkylaromatic compound. Useful free radical catalysts include peroxides such as t-butyl peroxide and t-amyl peroxide and hydroperoxides such as chloro-t-butyl hydroperoxide, cumene hydroperoxide and cyclohexane hydroperoxide. Diazo compounds and diacyl peroxides are similarly useful. Representative alkyl aromatic compounds include ethylbenzene, n-propylbenzene, n-butylbenzene, n-octylbenzene, n-decylbenzene, n-dodecylbenzene, ethylphenyl acetate, ethylnaphthalene, diethylbenzene, diethylbiphenyl, n-propylbiphenyl, and ethylthiophene. Dehydrochlorination of 1,1-dichloroethylbenzene or other such dihalo-compounds having a beta hydrogen will produce the corresponding 1-halostyrene which is employed in the process of the present invention for the preparation of the triaromatic bisphenols. The halo-compound, for instance 1,1-dichloroethylbenzene or 1-chlorostyrene, is added to the molten phenolic compound or, optionally, to the phenolic compound in solution, and reacted at a suitable temperature. The phenolic compound is preferably employed in excess to limit the formation of higher molecular weight phenolics. To form a bisphenol in good yield, the phenolation (reaction of phenolic compund with halo-compound) requires at least two moles of phenolic compound for each mole of the halo-compound. When the reaction is conducted by reacting a 1-halostyrene, trihalotoluene or dihalocyanotoluene with the phenolic compound the conditions are the same as when using the dihalo-compounds illustrated by 1,1-dichloroethylbenzene. When mixtures of suitable dihalo-compounds, trihalotoluenes, cyanodihalotoluenes and/or 1-halostyrenes are employed, the mole ratios and other conditions and parameters are the same as when using either of these reactants separately. It is advantageous to avoid water in the reaction between the phenolic compound and the halo-compound because in the presence of acid, the halo-compounds react with water to form acetophenone. Acetophenone, thus, may be present even though it is not a reactant in the process of the invention. To avoid this side-reaction it is preferred to dry or use anhydrous reagents, catalysts and solvents for the reaction. It is also advantageous to maintain an atmosphere inert to the reaction mixture or of catalytic acid such as hydrogen chloride rather than to allow air (with its moisture) to contact the reaction mixture. The reaction is preferably allowed to proceed to a preselected degree of completion, before recovery of product. Any degree of completion is suitable, but yield is improved by allowing the reaction to produce as much product as the reaction will produce under reaction conditions within convenient length of time. More preferably, a degree of completion corresponding to a yield of at least 80 percent is preselected. Most preferably, the preselected degree of completion is that corresponding to substantial disappearance of halo-compound, that is disappearance of at least 90 weight percent of the halo-compound, more preferably of all halo-compound detectable by laboratory means such as gas chromatography. Methods of recovering product bisphenols from reaction mixtures are within the skill in the art. Conveniently, when there is little excess phenolic compound remaining in the reaction mixture, a crystallization solvent is added to the reaction mixture to precipiate product. Advantageously, when excess phenolic compound is present, it is removed by means within the skill in the art before a crystallization solvent is added to precipitate the product. Convenient crystallization solvents include aromatic hydrocarbons such as toluene, ethylbenzene and chlorobenzene; chlorinated aliphatics such as chloroform and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; and esters such as diethyl carbonate and mixtures of these solvents. Crystallation is advantageously enhanced by cooling of the reaction mixture before or after addition of the crystallization solvent. Cooling alone is sometimes sufficient to cause precipitation of product without addition of crystallization solvent. Before crystallization hydrogen chloride is optionally, but preferably removed by means within the skill in the art such as distillation. The process of the invention advantageously produces triaromatic bisphenolic having a high percentage of para isomer (the hydroxyl group on a phenyl ring is para to the ring position of attachment of the carbon atom to which the three aromatic groups are attached). The mole ratio of para to ortho isomers is advantageously equal to or greater than at least 60:40, preferably at least 75:25, more preferably at least 90:10, most preferably at least 95:5. While the process of the invention generally produces products having these high ratios of para to ortho isomers, other methods of preparing the triaromatic bisphenols generally produce products having lower ratios of para to ortho isomers than those ratios produced in the practice of the invention. The following experiments are representative of the invention: Example 1 . Preparation of Bisphenol AP by reacting DCEB and phenol. Anhydrous phenol (3791.2 g, 40.28 moles) was transferred from a nitrogen-padded drum held at 78°C to a 5-L three-neck flask equipped with thermocouple, magnetic stirring bar, a nitrogen inlet and a 600 mL dropping funnel (vented through a scrubber to neutralize the HCl acid off-gas). A nitrogen atmosphere was maintained throughout the reaction by a continuous flow of nitrogen gas through the nitrogen inlet. The temperature was maintained with a heating mantle. The phenol was allowed to cool to 50°C and maintained at that temperature with a heating mantle. 1,1-Dichloroethylbenzene (DCEB) (700.2 g, 4.0 moles) was charged to the dropping funnel and addition was begun at a rate that will complete it in 4 hours. The phenol solution turned bright red immediately upon addition of DCEB and evolution of HCl (hydrochloric acid) began within a few minutes. The reaction mixture was stirred continually and held at the 50°C temperature for one hour after the addition was complete. A sample was analyzed by gas chromatography (G.C.) at this time to determine the completeness of the reaction. When completion of the reaction was indicated by disappearance of the peak corresponding to the halo-compound (DCEB), a distillation head was placed on the flask and the bulk of the phenol removed at aspirator pressure (ca. 50 mm Hg; 7 kPa). The reaction flaskwas then allowed to cool to room temperature and 2L of CCl₄ (carbon tetrachloride) was added with stirring. When this solution was cooled to room temperature and filtered, 904.8 g (78 percent of theoretical yield) of white crystals (m.p. 187-89) were obtained. The crystallized product was bis-1,1-(4′-hydroxyphenyl)-1-phenylethane (4,4′-Bisphenol AP) and contained no detectable bis-1-1-(2,4′ hydroxyphenyl)-1-phenylethane (2,4′-Bisphenol AP). Examples 2-15 . Preparation of bisphenol AP employing different parameters. Other experiments were conducted in the manner of Example 1 employing different temperatures, ratios of phenol to 1,1-dichloroethylbenzene, and other solvents. In some examples, additional HCl was supplied to the reaction mixture by sparging the mixture with HCl to the point of saturation. Conditions of the reactions and the results are shown in Table I. Examples 16 and 17 . Preparation of bisphenol AP by reacting α-chlorostyrene with phenol. In the manner of Example 1, α-chlorostyrene (α-CS) was substituted for DCEB in the reaction with phenol to make the Bisphenol AP. Conditions and results are shown in Table II. Example 18 . Preparation of bisphenol AP by reacting DCEB and phenol. In yet another preparation, anhydrous molten phenol (4350.6 g, 46.22 moles) and 900 mL CCl₄ were placed in a 5-L flask fitted in the manner of Example 1. The mixture was allowed to cool to 30°C while being sparged with HCl, and DCEB (712.46 g, 4.07 moles) was added dropwise to the stirring mixture over a 5-hour period. The mixture was allowed to stir an additional 45 min. or until G. C. analysis showed the reaction to be complete. Excess phenol was removed by distillation and 2500 mL of chlorobenzene was added with stirring and the mixture was allowed to cool to room temperature. Crystals of product were filtered, and washed with CCl₄. After drying in a vacuum oven at 120°C overnight a 92 percent yield of bisphenol AP (1105.48 g) was obtained based on the starting DCEB. The product was 99.6 percent 4,4′-bisphenol AP. The crystallized product contained no detectable 2,4′-bisphenol AP. Example 19 . Preparation of bisphenol AP by reacting α-chlorostyrene and phenol in ethylbenzene solvent. To a quantity (957.5g) of phenol at 40°C was added 115 g of ethylbenzene. Anhydrous HCl was bubbled through the mixture for one hour and used to bring the pressure to 10 psig (70 kPa gauge). The solution was agitated while 201.3g of α-chlorostyrene in 300g ethylbenzene was continuously fed into the reaction mixture (one-half over a 5-hour period and the remainder in an additional 7 hour period). The temperature of the reaction mixture was lowered gradually to 32°C over the first 80 minutes and maintained there for the remainder of the 12-hour reaction period. Analysis of the reaction mixture by liquid chromatography showed a selectivity to bisphenol AP of 91 percent (98.9 percent 4,4'-bisphenol AP) based on α-chlorostyrene. The actual yield of product recovered by crystallization was 89 percent (100 percent 4,4'-bisphenol AP), based on the α-chlorostyrene. Example 20. Using 1,1,1-Trichlorotoluene to prepare 1,1,1-Tris(4-Hydroxyphenyl)toluene In a manner of Example 1, benzotrichloride (otherwise 1,1,1-trichlorotoluene) (0.35 moles, 69.0 g) was added to phenol (7.24 moles, 681.4 g) dissolved in carbon tetrachloride (2.59 moles, 398.5 g) over a 4 hour period. The reaction mixture turned bright red and vented HCl immediately upon the addition of the first drops of benzotrichloride. The excess phenol was distilled at aspirator vacuum and the product was crystallized from diethylcarbonate. Analysis of Proton nuclear magnetic resonance (HNMR) showed peaks from a tetramethylsilane standard of δ6.8 (q,12H), δ7.1(s,5H), δ8.5(s,3H) ( q= quartet, s= singlet) corresponding to a structure of 1,1,1-tris(4-hydroxyphenyl) toluene. The melting point was measured as 272-275°C.

Claims: A process for the preparation of triaromatic bisphenols characterized by the reaction of a phenolic compound with at least one halo-compound selected from aromatic compounds having an (α,α-dihalo)alkyl or (α-halo)alk-1-enyl substituent with at least one β-hydrogen atom in said alkyl or alkenyl moiety, a trihalomethyl substituent or a dihalocyanomethyl substituent. A process as claimed in Claim 1, wherein said phenolic compound is selected from phenol, naphthols, hydroxybiphenyls, alkylphenols, dialkylphenols, thiophenol, nitrophenols and halophenols. A process as claimed in Claim 2, wherein said phenolic compound is phenol optionally substituted with C₁-C₅ alkyl. A process as claimed in any one of the preceding claims, wherein said halo-atom(s) are chlorine. A process as claimed in Claim 4, wherein the chloro-compound is selected from 1,1,1-trichlorotoluene and 1-cyano-1,1-dichlorotoluene. A process as claimed in Claim 4, wherein the chloro-compound is selected from 1-chlorostyrene and 1,1-dichloroethylbenzene and mixtures thereof. A process as claimed in Claim 6, wherein the phenolic compound is phenol and the bisphenol is bis-1,1(4-hydroxyphenyl)-1-phenylethane. A process as claimed in any one of the preceding claims, wherein the ratio of reactants is at least two moles of phenolic compound per mole of halo-compound. A process as claimed in Claim 8, wherein the phenolic compound is used in an amount in excess of the stoichiometric amount. A process as claimed in Claim 9, wherein the molar ratio of phenolic compound to halo-compound is from 5/1 to 25/1. A process as claimed in any one of the preceding claims, wherein an acid catalyst is used. A process as claimed in Claim 11, wherein said acid catalyst is a hydrogen halide. A process as claimed in Claim 12, wherein the phenolic compound is admixed with the hydrogen halide prior to contact with the halo-compound. A process as claimed in Claim 12 or Claim 13, wherein the hydrogen halide is hydrogen chloride. A process as claimed in any one of Claims 12 to 14, wherein the hydrogen halide provides a reaction pressure greater than 0.1 MPa (1 atmosphere). A process as claimed in Claim 15, wherein said reaction pressure is 0.1 to 1 MPa (1 to 10 atmosphere). A process as claimed in any one of the preceding claims, wherein excess phenolic compound serves as a solvent. A process as claimed in any one of Claims 1 to 16, wherein a chlorinated hydrocarbon or an aromatic hydrocarbon is used as a solvent. A 1,1,1-tris(4-hydroxyphenyl) toluene having no additional substituents in said 4-hydroxyphenyl groups, obtainable by a process as claimed in Claim 1 and containing at most 40 mole percent 2-hydroxyphenyl isomers (based on the combined amounts of 2- and 4- hydroxyphenyl isomers). A 1,1,1-tris(4-hydroxyphenyl) toluene as claimed in Claim 19 containing at most 25 mole percent 2-hydroxyphenyl isomers (based on the combined amounts of 2- and 4-hydroxyphenyl isomers). A 1,1,1-tris(4-hydroxyphenyl) toluene as claimed in Claim 20 containing at most 10 mole percent 2-hydroxyphenyl isomers (based on the combined amounts of 2- and 4-hydroxyphenyl isomers). A 1,1,1-tris(4-hydroxyphenyl) toluene as claimed in Claim 21 containing at most 5 mole percent 2-hydroxyphenyl isomers (based on the combined amounts of 2- and 4-hydroxyphenyl isomers). A 1,1,1-tris(4-hydroxyphenyl) toluene as claimed in any one of Claims 19 to 22, wherein the phenyl ring of the toluene group is unsubstituted. A polymer derived from a bisphenol characterized in that said bisphenol comprises a 1,1,1-tris(4-hydroxyphenyl) toluene as defined in any one of Claims 19 to 23.

Inventors: RICHEY W FRANK, TASSET EMMETT L, WALTERS MARLIN E, RICHEY, W. FRANK, TASSET, EMMETT L., WALTERS, MARLIN E.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1991
Main classification: C07C39
IPC codes: C07B61, C07C39, C07C37, B01J27