S,S'-BIS-( alpha , alpha '-DISUBSTITUTED- alpha "-ACETIC ACID)-TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR - CHAIN TRANSFER AGENT - TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME

Abstract: A S,S'-bis-( alpha , alpha '-disubstituted- alpha "-acetic acid)-trithiocarbonates and derivatives thereof can be used as an initiator, chain transfer agent, or terminator for polymerization of monomers such as free radical polymerizable monomers. Homopolymers, copolymers, and the like as well as block copolymers can be made utilizing the trithiocarbonate compound such as in a living free radical plymerization as well as to form telechelic polymers.

Description: s,s'-Bis-(α, ' - DISUBSTITUTED - or - ACETIC ACID) - TRITHIOCARBONATES AND DERIVATIVES AS INITIATOR - CHAIN TRANSFER AGENT - TERMINATOR FOR CONTROLLED RADICAL POLYMERIZATIONS AND THE PROCESS FOR MAKING THE SAME FIELD OF THE INVENTION The present invention relates to s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonates and derivatives thereof, as well as a process for making the same Moreover, other functional end groups can be derived from the carboxy c acid end groups The compounds can be utilized as initiators, chain transfer agents, or terminators for controlled free radical polymerizations Free radical polymerizations utilizing s,s'-bιs-(α, ' - disubstituted - α" - acetic acid) - tπthiocarbonate compounds generally form teleche c polymers If an initiator other than the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compound is also utilized, a polymer having a single functional end group is formed in proportion to the amount of the initiator to the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compound utilized BACKGROUND OF THE INVENTION Although several members of the class of organic thiocarbonates have been known for many years and various routes have been employed for their synthesis, the s,s'-bιs-(α, ' - disubstituted - " - acetic acid) - tπthiocarbonate compounds of the present invention have not been disclosed Tπthiocarbonate compounds have been claimed for various applications, such as pesticides for agriculture, and also as lubricating oil additives Traditional methods of producing block copolymers, such as by living polymerization or the linking of end functional polymers, suffer many disadvantages, such as the restricted type monomers which can be utilized, low conversion rates, strict requirements on reaction conditions, and monomer purity Difficulties associated with end linking methods include conducting reactions between polymers, and problems of producing a desired pure end functional polymer The s,s'-bιs-(α, ' - disubstituted - α" - acetic acid) - tπthiocarbonate compounds of the present invention can alleviate the above noted problems and difficulties when utilized in free radical polymerizations The prior art WO98/01 478 reference discloses the use of thiocarboπates to conduct living free radical polymerizations The reference is limited to alkyl and benzyl functional groups, and is unable to make any aryl or carboxy c acid substituted tπthiocarbonates with general methods known to the art Synthesis, p 894 ( 1 986), J Chemical Research (Synopsis) p478 ( 1 995) , and Synthetic Communications, Vol 1 8, p 1 531 ( 1 988) We have also found the conversion for the dibenzyl derivatives disclosed in their example 26 to be very slow compared to the present invention when polymerizing acrylate, as can be seen in the Example section of this application SUMMARY OF THE INVENTION The present invention relates to s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonates which have the general formula R 1 S R 1 HOOC- C- ; — c — s — c • COOH R 2 R 2 where R 1 and R 2 are set forth below, to derivatives thereof, and to a process for making the same The s,s'-bιs-( , α - disubstituted - α' - acetic acid) tπthiocarbonate compounds can generally be formed from carbon disulfide, a haloform, and a ketone in a strong base, such as sodium hydroxide, followed by acidification. The s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) tπthiocarbonate compounds can be used as iπifertors, i.e. as initiators and chain transfer agents, and/or chain terminators or as a chain-transfer agent during polymerization The compounds can thus be utilized to control free radical polymerization thermally and chemically to give narrow molecular weight distributions Polymerization of monomers can be in bulk, in emulsion, or in solution. Block copolymers can be made if two or more monomers are polymerized in succession. The difunctional acid end groups present can further react with other reactive polymers or monomers to form block or random copolymers. Free radical polymerizations utilizing the s,s'-bιs-(α, ' - disubstituted - α" - acetic acid) - tπthiocarbonate compounds generally form teleche c polymers. If an initiator other than the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compound is also utilized, a polymer having a single functional end group is formed in proportion to the amount of said other initiator to the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compound utilized. DETAILED DESCRIPTION OF THE INVENTION The s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate and derivatives prepared by the processes disclosed later herein generally can be described by the formula R 1 S R 1 HOOC — J C. — S — C " — S — C ! — COOH I I R 2 R 2 wherein R 1 and R 2 , independently, can be the same or different, and can be linear or branched alkyls having from 1 to about 6 carbon atoms, or a C, to about C 6 alkyl having one or more substituents, or one or more aryls or a substituted aryl group having 1 to 6 substituents on the aryl ring, where the one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms; or an aryl; or a halogen such as fluorine or chlorine; or a cyano group; or an ether having a total of from 2 to about 20 carbon atoms such as methoxy, or hexanoxy; or a nitro; or combinations thereof. Examples of such compounds include s,s'-bιs- 2-methyl-2-propanoιc acid-tπthiocarbonate and s,s'-bιs-(2-phenyl-2- propanoic acιd)-trιthιocarbonate. R 1 and R 2 can also form or be a part of a cyclic ring having from 5 to about 1 2 total carbon atoms. R 1 and R 2 are preferably, independently, methyl or phenyl groups. The abbreviated reaction formula for the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonates of the present invention can be generally written as follows: O OH The process utilized to form the s,s'-bιs-(α, α' - disubstituted - " - acetic acid ) - tπthiocarbonate compounds of the present invention is generally a multi-step process and includes combining the carbon disulfide and a base whereby an intermediate tπthio structure is formed, see I. II. Ill, and IV. Ketone can serve as solvent for the rarbon disulfide/base reaction and thus can be added in the first step of the reaction In the second step of the reaction, the haloform, or haloform and ketone, or a α-tπhalomethyl-α-alkanol are added to the tπthio intermediate mixture and reacted in the presence of additional base, see V. VI, and VII. The formed reaction product, see IX. is subsequently acidified, thus completing the reaction and forming the above described s,s'-bιs-( , ' - disubstituted - α" - acetic acid) - tπthiocarbonate compound, see X. The reaction is carried out at a temperature sufficient to complete the interaction of the reactants so as to produce the s,s'-bιs- (α, α' - disubstituted - α' - acetic acid) - tπthiocarbonate compound in a desired time The reaction can be carried out at any temperature within a wide range from about the freezing point of the reaction mass to about the reflux temperature of the solvent The reaction temperature is generally from about minus 1 5°C to about 80°C, desirably from about 0°C to about 50°C, and preferably from about 1 5°C to about 35°C, with room temperature being preferred The reaction can be performed at atmospheric pressure The reaction time depends upon several factors, with the temperature being most influential The reaction is generally complete within 20 hours and preferably within 1 0 hours A phase transfer catalyst is preferably utilized if a solvent is used in the reaction Examples of solvents are set forth herein below The ketone utilized in the reaction may double as a solvent, and therefore no catalyst usually is needed The amount of phase transfer catalyst, when utilized in the present invention, is generally from about 0 1 mole percent to about 1 0 mole percent, desirably from about 0.5 mole percent to about 5 mole percent and preferably from about 2 mole percent to about 4 mole percent per mole of carbon disulfide The phase transfer catalysts can be polyether, and/or an onium salt including a quaternary or tertiary organic compound of a group VA or VIA element of the Periodic Table and salts thereof Most preferred are quaternary amines, and salts thereof "Onium salts" more particularly refer to tertiary or quaternary amines and salts such as are generally used in the phase transfer catalysis of heterogeneous reaction in immiscible liquids The general requirement for the onium salt chosen is that it be soluble in both the organic and aqueous phases, when these two liquid phases are present, and usually a little more soluble in the organic phase than the aqueous phase. The reaction will also proceed with a phase transfer catalyst when there is only a single organic liquid phase present, but such a reaction is less preferable than one in which both aqueous and organic liquid phases are present. A wide variety of onium salts is effective in this ketoform synthesis. The onium salts include the well-known salts, tertiary amines and quaternary compounds of group VA elements of the Periodic Table, and some Group VIA elements such as are disclosed in the U.S. Patent No. 3, 992,432 and in a review in Angewandte Chemie, International Edition in English, 1 6 493-558 (August 1 977) . Discussed therein are various anion transfer reactions where the phase transfer catalyst exchanges its original ion for other ions in the aqueous phase, making it possible to carry our chemistry there with the transported anion, including OH-ions. The onium salts used in this synthesis include one or more groups having the formula (R n Y) " X , wherein Y is either a pentavalent ion derived from an element of Group VA, or a tetravalent ion derived from an elemeni of Group VIA; R is an organic moiety of the salt molecule bonded to Y by four covalent linkages when Y is pentavalent, and three covalent linkages when Y is tetravalent; X is an anion which will dissociate from the cation (R n Y) ' in an aqueous environment. The group (R n Y) " X may be repeated as in the case of dibasic quaternary salts having two pentavalent Group VA ions substituted in the manner described. The preferred onium salts for use in the invention have the formula (R A R B R C R D Y * )X wherein Y is N or P, and R 1 - R 4 are monovalent hydrocarbon radicals preferably selected from the group consisting of alkyl, alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl moieties or radicals, optionally substituted with suitable heteroatom-containing functional groups. The onium salts are generally selected to be less preferentially less soluble in the less polar of the two distinct liquid phases. Any of the salts disclosed in the U.S. Patent No. 3,992,432 will be found effective, but most preferred are those in which the total number of carbon atoms in R A ,R B ,R C , and R D cumulatively range from about 1 3 to about 57, and preferably range from about 1 6 to about 30. Most preferred onium salts have Y = N, and hydrocarbon radicals where R A is CH 3 , and R B , R c , and R D are each selected from the group consisting of n-C 2 H 5 , n-C 4 H 5 ; n-C 5 H ; mixed C 5 H 17 ; n-C 12 H 25 ; n-C 18 H 37 ; mixed C 8 -C 10 alkyl; and the like. However, R A may also be selected from C 2 H 5 n-C 3 H 7 and n-C 4 H 9 benzyl. Various counteπons may be used, including Cl " , Br , I " , N0 3 , S0 4 2 , HS0 4 and CH 2 C0 2 . Most preferred is Cl ' . The tertiary amines or tπamines useful as phase transfer catalysts in this synthesis include the alkyl amines and the aryldialkylamines, exemplified by tπbutylamiπe and phenyldibutylamine respectively, which are commonly available, wherein each alkyl may have from 1 to about 1 6 carbon atoms. The poiyethers useful as catalysts in this synthesis include cyclic poiyethers such as the crown ethers, disclosed in Agenwandte Chemie, supra, and acyclic poiyethers having the formula R-0-R E wherein R and R E are, independently, alkyls having from 1 to about 1 6 carbon atoms, or alkyl containing substituted functional groups such as hydroxy, sulfur, amine, ether, etc. Most preferred acyclic poiyethers have the formula R - (OCH 2 CH 2 ) , OR" wherein R is an alkyl having from 1 to about 1 6 carbon atoms R" is an alkyl having from 1 to about 1 6 carbon atoms, or H, and r is an integer in the range from 0 to about 300. Most preferred are commonly available poiyethers such as: tetraethylene glycol dimethyl ether; polyethylene oxide (mol wt. About 5000); poly(ethylene glycol methyl ether); 1 ,2-dιmethoxyethane; diethyl ether, and the like. Polyether catalysts are especially desirable in this ketoform synthesis because they are directive so as to produce a preponderance of the desired symmetrically substituted isomer, in a reaction which is remarkably free of undesirable byproducts, which reaction proceeds with a relatively mild exotherm so that the reaction is controllable. The organic solvent may be any solvent in which the reactants are soluble and include hydrohalomethylenes, particularly hydrochloromethylenes, sulfolane, dibutyl ether, dimethyl sulfone, dnsopropyl ether, di-n-propyl ether, 1 ,4-dιoxane, tetrahydrofuran, benzene, toluene, hexane, carbon tetrachloride, heptane, mineral spirits and the like Most preferred solvents are heptanes and mineral spirits Solvent is generally utilized in an amount generally from about 1 0 to about 500 percent and preferably from about 50 percent to about 200 percent based on the total weight of the reactants. 'nsofar as the reactive components are concerned, any of various ketones having the general formula O II R 1 — C R 2 can be employed in the synthesis, wherein R 1 and R 2 are described herein above. As carbon disulfide is the controlling agent in the reaction, the ketone is generally used in an amount from about 1 1 0 mole percent to about 2,000 mole percent per mole of carbon disulfide. When the ketone is used as a solvent, it is generally utilized in an amount of from about 1 50 mole percent to about 300 mole percent, and preferably from about 1 80 mole percent to about 250 mole percent per mole of carbon disulfide. The alkali bases suitable for use in the synthesis of the present invention include, but are not limited to, sodium hydroxide and potassium hydroxide. The base is utilized in an amount generally from about 5 times to about 1 5 times the number of moles of carbon disulfide and preferably from about 6 to about 1 0 times the number of moles of carbon disulfide utilized in the reaction. The acids used in the acidification step include, but are not limited to, hydrochloric acid, sulfuπc acid, phosphoric acid, etc. The acids are utilized in amounts suitable to make the aqueous solution acidic. The haloform of the present invention has the general formula CHX 3 wherein X is, independently, chlorine or bromine. The amount of haloform used in the present invention is generally from about 1 1 0 mole percent to about 2000 mole percent, desirably from about 1 50 mole percent to about 300 mole percent, and preferably 1 80 mole percent to about 250 mole percent per mole of carbon disulfide. Examples of haloforms include, but are not limited to, chloroform and bromoform, and chloroform is the preferred haloform of the present invention. Alternatively, instead of adding both a haloform and a ketone, to the reaction mixture, an α-tπhalomethyl-α-alkanol can be substituted therefore The amount of α-tπhaiomethyl-α-alkanol utilized in the reaction generally is from about 1 1 0 mole percent to about 2000 mole percent, desirably is from about 1 50 mole percent to about 300 mole percent, and preferably is from about 1 80 mole percent to about 250 mole percent per moie of carbon disulfide. The general formula of the -tπhalomethyl-α-alkanol is generally represented as follows- HO CX, R 1 wherein X, R 1 and R 2 are defined above While not wishing to be limited to any particular mechanism, it is believed that the specific mechanism for the reaction process is as follows. Initially, the carbon disulfide and sodium hydroxide are reacted. CS, 2NaOH Na ' 0 — C Na " + H,O il CS, ▼ s III Na " -0 — C — S — C — S — Na + 2 NaOH S IV Na " C - 0 Na " Na ¬ — S — Na " + H 2 0 (tπthio intermediate) In the subsequent step of the reaction, the chloroform is reacted with the ketone as follows: HCCI 3 + NaOH H 2 0 + Na + — CC V ( 1 -dιsubstιtuted-2-dic loroepoxide) Then, the following is reacted: R' CIOC C S — C — S — C — COCI + 2NaCI VIII 4 NaOH R 1 IX Na * OOC - C — S — C— S — C — COO Na " + 2NaCI + 2H 2 0 R 2 R 2 (dicarboxylate salt) 2HCI R 1 S R 1 I II I HOOC C S — C — S — C — COOH + NaCI : I I R 2 R 2 The overall reaction is as follows: 0 || XI 2CS 2 + 2CHC + 2R 1 - C - R 2 + 1 0NaOH + 2HCI ► R 1 S R 1 S XII HOOC- C - S -C -S- C- COOH + Na * 0 -C -O Na + + 8 NaCI + 6H 2 0 The s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compounds produced by the present invention can generally be classified as inifertors, meaning that they act as both a chain transfer agent and an initiator The use of other types of inifertors for block copolymers was discussed by Yagei and Schnabel in Progress in Polymer Science J 55 1 ( 1 990) and is hereby fully incorporated by reference. Thus, the compounds of the present invention can be utilized as initiators to initiate or start the polymerization of a monomer. They can also act as a chain transfer agent, which interrupts and terminates the growth of a polymer chain by formation of a new radical which can act as a nucleus for forming a new polymer chain. The compounds can also be utilized as terminators in that when most of initiating radicals and monomers are consumed, the compounds are incorporated in the polymers as a dormant species. Desirably though, another compound, such as those listed herein below, is often used as an initiator in the free radical polymerization process as described herein below, and the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds of the present invention will act as a chain- transfer agent. The s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds of the present invention can be used as chain transfer agents in a free radical polymerization process to provide polymerizations which have living characteristics and polymers of controlled molecular weight and low polydispersity, as well as for forming telechelic polymers. A living polymerization is a chain polymerization which proceeds in the absence of termination and chain transfer The following experimental criteria can be utilized to diagnose a living polymerization. 1 . Polymerization proceeds until all monomer has been consumed. Further addition of monomer results in continued polymerization. 2. The number average molecular weight, M n (or X n , the number average degree of polymerization) , is a linear function of conversion. 3 The number of polymer molecules (and active centres) is constant and independent of conversion. 4. The molecular weight can be controlled by the stoichiometry of the reaction. 5. Narrow molecular weight distribution polymers are produced. 6 Chain-end functionalized polymers can be prepared in quantitative yields. 7. In radical polymerization, the number of active end groups should be 2, one for each end. Besides those mentioned above, other criteria can also help to determine the living character of polymerization. For radical living polymerization, one is the ability of the polymer isolated from the first step of polymerization to be used as a macroinitiator for the second step of a polymerization in which block copolymers or grafted polymers are ultimately formed. To confirm the formation of block copolymers, measurements of molecular weights and a determination of the structure of the blocks are employed . For structure measurements, the examination of NMR or IR signals for the segments where individual blocks are linked together and a determination of the end groups are both very important. In radical polymerization, only some of the criteria for living polymerizations are actually fulfilled. Due to their ability to undergo further polymerization, these types of polymers can also be called 'reactive polymers' . A more detailed description of living polymerization can be found in "Living Free-Radical Block Copolymeπzation Using Thio-lnifertors", by Anton Sebenik, Progress in Polymer Science, vol. 23, p. 876, 1 998. The living polymerization processes can be used to produce polymers of narrow molecular weight distribution containing one or more monomers sequences whose length and composition are controlled by the stoichiometery of the reaction and degree of conversion Homopolymers, random copolymers or block polymers can be produced with a high degree of control and with low polydispersity. Low polydispersity polymers are those with polydispersities that are significantly less than those produced by conventional free radical polymerization. In conventional free radical polymerization, polydispersities (polydispersity is defined as the ratio of the weight average to the number average molecular weight M w /M n ) of the polymers formed are typically greater than 2.0. Polydispersities obtained by utilizing the s,s'-bιs-( , ' - disubstituted - α" - acetic acid) - trithiocarbonate compounds and derivatives thereof of the present invention are preferably 1 .75 or 1 .5, or less, often 1 .3 or less, and, with appropriate choice of the chain transfer agent and the reaction conditions, can De 1 .25 or less. When the s,s'-bιs-(α, α' - disubstituted - " - acetic acid) - trithiocarbonates compounds are utilized only as chain-transfer agents, the polymerization can be initiated with other initiators at lower temperature while yielding polymers with similarly controlled fashion. Free radical polymerizations utilizing the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds as both initiators and chain transfer agents generally form telechelic polymers. When an initiator other than the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound is also utilized, a polymer having a single functional end group is formed in proportion to the amount of said other initiator to this s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound utilized. The free radical living polymerization process of the invention can be applied to any monomers or monomer combinations which can be free-radically polymerized. Such monomers include one or more conjugated diene monomers or one or more and vinyl containing monomers, or combinations thereof The diene monomers have a total of from 4 to 1 2 carbon atoms and examples include, but are not limited to, 1 ,3-butadιne, isoprene, 1 , 3-pentadιene, 2,3-dιmethyl- 1 -3-butadeιne, 2-methyl- 1 ,3-pentadιene, 2, 3-dιmethyl- 1 ,3-pentadιene, 2-pheπyl- 1 , 3-butadιene, and 4, 5-dιethyl- 1 ,3-octadιent:, and combinations thereof The vinyl containing monomers have the following structure- CH 2 = ~R « where R 3 comprises hydrogen, halogen, C, to C 4 alkyl, or substituted C-, - C 4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR 5 ) , carboxy, acyloxy, aroyloxy(0 2 CR 5 ), alkoxy-carbony!(C0 2 R 5 ) , or aryloxy-carbonyl; and R 4 comprises hydrogen, R 5 , C0 2 H, C0 2 R 5 , COR 5 , CN, CONH 2 , CONHR 5 , 0 2 CR 5 , OR 5 , or halogen. R 5 comprises C, to C 18 alkyl, substituted C, - C 18 alkyl, C 2 - C 18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy, (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, sicyaπato, cyano, silyl, halo and dialkylamino. Optionally, the monomers comprise maleic anhydride, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclopolymerizable monomers. Monomers CH 2 = CR 3 R 'i as used herein include C, - C 8 acrylates and methacrylates, acrylate and methacrylate esters, acrylic and methacrylic acid, styrene, α methyl styrene, C, , - C 1 2 alkyl styrenes with substitute groups both either on the chain or on the ring, acrylamide, methacrylamide, and methacrylonitrile, mixtures of these monomers, and mixtures of these monomers with other monomers. As one skilled in the art would recognize, the choice of comonomers is determined by their steπc and electronic properties. The factors which determine copolymeπzabi ty of various monomers are well documented in the art. For example, see: Greenley, R.Z. , in Polymer Handbook, 3 rd Edition (Braπdup, J., and Immergut, E. H. Eds.) Wiley: New York, 1 989 ρll/53. Specific monomers or comonomers include the following: methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene. methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile. styrene, functional methacrylates, acrylates and styrenes selected from glycidyl methacrylate, 2-hydroxyethyl ,methacrylιate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), N ,N-dιmethylamιnoethyl methacrylate, N, N- diethylaminoethyl methacrylate, triethyleneglycol methacrylate, itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrviate (all isomers) , hydroxybutyl acrylate (all isomers) , N,N- dimethylaminoethyl acrylate, N,N-dιethylamιnoethyl acrylate, triethyleneglycol acrylate, methacrylamide, N-methylacrylamide, N,N- dimethylacrylamide, N-terbtbutylmethacryiamide, N-n- butylmethacrylamide, N-methylolmethacrylamide, N- ethylotmethacrylamide N-tert-butyiacrylamide. N-n-butylacrylamide, N- methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (all isomers), dethylaminostyrene (all isomers), alpha-methylviπyl benzoic acid (all isomers) , dethylamino alpha-methylstyrene (all isomers) p-vmylbenzene sulfonic acid, p-vmylbenzene sulfonic sodium salt, tπmethoxysilylpropyl methacrylate, tπethoxysilylpropyl methacrylate, tπbutoxysilyipropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylslylpropyl methacrylate, dibutoxymethylsilypropyl methacrylate, dnsopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxy, silylpropyl methacrylate, dnsopropoxysilylpropyl methacrylate, tπmethoxysilylpropyl acrylate, tπethoxysifylylpropyl acrylate, tπbutoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, dnsopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, dnsopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-pheπylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N- vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, and propylene, and combinations thereof Preferred monomers are C 1 - C 8 acrylates , C, - C 8 methacrylates, styrene, butadiene, isoprene and acrylonitrile. As noted above, in order to initiate the free radical polymerization process, it is often desirable to utilize an initiator as a source for initiating free radicals Generally, the source of initiating radicals can be any suitable method of generating free radicals such as the thermally induced homolytic scission of a suitable compound(s) (thermal initiators such as peroxides, peroxyesters, or azo compounds), the spontaneous generation from monomer (e.g., styrene), redox initiating systems, photochemical initiating systems or high energy radiation such as electron beam, X- or gamma-radiation The initiating system is chosen such that under the reaction conditions there is no substantial adverse interaction of the initiator or the initiating radicals with the transfer agent under the conditions of the experiment The initiator should also have the requisite solubility in the reaction medium or monomer mixture The s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds of the invention can serve as an initiator, but the reaction must be run at a higher temperature Therefore, optionally it is desirable to utilize an initiator other than the s,s'-bιs-( , α' - disubstituted - α" - acetic acid) - trithiocarbonates compounds of the present invention Thermal initiators are chosen to have an appropriate half-life at the temperature of polymerization. These initiators can include one or more of the following compounds. 2,2'-azobιs(ιsobutyronιtπle)(AIBN) , 2,2'-azobιs(2-cyano-2- butane), dimethyl 2,2'- azobisdimethylisobutyrate, 4,4'-azobιs(4- cyanopentanoic acid) , 1 , 1 '-azobιs(cyclohexanecarbanιtπle) , 2-(t- butylazo)-2-cyanopropane, 2,2 - azobιs[2-methyl-N-( 1 , 1 )- bιs(hydoxymethyl)-2-hydroxyethyl] propionamide, 2,2'-azobιs[2-methyl- N-hydroxyethyl)]-propιonamιde, 2,2'-azobιs(N,N'- dimethyleneisobutyramidine) dihydrochloπde, 2,2'-azobιs(2- amidinopropane) dihydrochloπde, 2,2 '-azobιs(N,N'- dimethyleneisobutyramine), 2,2'-azobιs(2-methyl-N-[ 1 , 1 - bιs(hydroxymethyl)-2-hydroxyethyl] propionamide), 2,2'-azobιs(2-methyl- N-[ 1 , 1 -bιs(hydroxymethyl) ethyl] propionamide), 2,2'-azobιs[2-methyl- N-(2-hydroxyethyl) propionamide], 2,2'-azobιs(ιsobutyramιde) dehydrate, 2, 2'-azobιs(2,2,4-tπmethylpentane), 2,2 '-azobιs(2-methylpropane) , t- butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate, t- butylperoxyneodecanoate, t-butylperoxy isobutyrate, t-amyl peroxypivalate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroylperoxide, potassium peroxydisulfate, ammonium peroxydisulfate, di-t-butyl hyponitπte dicumyl hyponitπte Photochemical initiator systems are chosen to have the requisite solubility in the reaction medium or monomer mixture and have an appropriate quantum yield for radical production under the conditions of the polymerization Examples include benzoin derivatives, benzophennne, acyl phosphine oxides and photo-redox systems production under the conditions of the polymerization, these initiating systems can include combinations of the following oxidaπts and reductants oxidancs potassium peroxydisuffate, hvdrogen peroxide, t-butyl hydroperoxide reductants iron ( 1 1 ), titanium ( 1 1 1 ), potassium thiosulfite, potassium bisulfite Other suitable initiating systems are described in recent texts. See, for example, Moad and Solomon "The Chemistry of Free Radical Polymerization" . Pergamon, London. 1 995. pp 53-95. The preferred initiators of the present invention are 2,2'- azobιs(ιsobutyronιtrιle)(AIBN), or 4,4'-azobιs(4-cyanopentanoιc acid), or 2,2'-azobιs(2-cyano-2-butane) , or 1 , 1 '-azobιs(cyclohexanecarbaπιtrιle). The amount of initiators utilized in the polymerization process can vary widely as generally from about .001 percent to about 99 percent, and desirably from about 0.01 percent to about 50 or 75 percent based on the total moles of chain transfer agent utilized. Preferably small amounts are utilized from about 0.1 percent to about 5, 1 0, 1 5, 20, or 25 mole percent based on the total moles of chain transfer agent utilized, i.e. said s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds. In order to form polymers which are predominately telechelic, initiators other than the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds are utilized in lesser amounts, such as from about 0.001 percent to about 5 percent, desirably from about 0.01 percent to about 4.5 percent, and preferably from about 0 1 percent to about 3 percent based on the molar equivalent to the total moles of chain transfer agent utilized. Optionally, as noted above, solvents may be utilized in the free radical polymerization process. Examples of such solvents include, but are not limited to, C 6 - C, 2 alkanes, toluene, chlorobenzene, acetone, t-butyl alcohol, and dimethylformamide. The solvents are chosen so that they do not chain transfer themselves. The amount of solvent utilized in the present invention polymerization process is generally from about 1 0 percent to about 500 percent the weight of the monomer, and preferably from about 50 percent to about 200 percent the weight of the monomer utilized in the polymerization. As stated above, it is preferable to utilize the s,s'-bιs-(α, α' - disubstituted - " - acetic acid) - trithiocarbonate compounds of the invention as chain transfer agents in the free radical polymerization process. The amount of chain transfer agent (CTA) utilized depends on the desired molecular weight of the polymer to be formed and can be calculated as known by one skilled in the art. A formula for calculating the amount of chain transfer agent is as follows: Mπ of polymer = Weight of monomer X molecular weight CTA - molecular weight of CTA Weight of CTA While not wishing to be limited to any particular mechanism, it is believed that the mechanism of the free radical living polymerization process is as follows when using a vinyl monomer R 1 R 2 (A) R 1 XVI - C — H,C4-C —COOH R 1 R 3 S R 1 XIX I I . II I HOOC — C - -CH 2 — C -S — C — ShC -CH : C — COOH R 2 R ύ R 2 Alternatively, the reaction can proceed as follows: R 1 R R 1 XXI R 3 R 3 R 1 XXII In — CH 2 C — COOH R * R 2 As can be seen from the above mechanism, polymers having two different structures, see XIX and XXII, can be formed. The resulting polymers are either telechelic polymers (formed by the trithiocarbonate compounds of the present invention) with identical functional groups at the ends of the chain, or a polymer having a single functional end group and also an initiator terminated chain (formed by using a conventional initiator such as AIBN) . As stated above, the ratios between the resulting polymers can be controlled to give desired results and generally depends on the amount of initiator utilized. Obviously, if the initiator is the only s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound of the present invention, the resulting polymers are always telechelic. The greater the amount of the other initiator utilized, proportionally decreases the amount of telechelic polymers formed. Generally, the amount of the repeat group m, m', m ", n, n', or n", is generally from about 1 to about 1 0,000, desirably from about 5 to about 500, and preferably from about 1 0 to about 200. Inasmuch as one or more vinyl monomers and/or one or more diene monomers can be utilized, it is to be understood that repeat groups of the polymers of the present invention are generally indicated by formulas XIX and XXII and can be the same or different. That is, random copolymers, terpolymers, etc., can be formed within either of the two repeat groups noted, as well as block copolymers which can be formed by initially adding one monomer and then subsequently adding a different monomer (e.g. an internal block copolymer) . The polymers formed by the present invention can be generally represented by the following formula: R R W HOOC- C C-COOH I R R 2 wherein such monomers are described herein above. Of course, the above formula can contain an initiator end group thereon as in XXII The reaction conditions are chosen as known to one skilled in the art so that the temperature utilized will generate a radical in a controlled fashion, wherein the temperature is generally from about room temperature to about 200°C The reaction can be run at temperatures lower than room temperature, but it is impractical to do so. The temperature often depends on the initiator chosen for the reaction, for example, when AIBN is utilized, the temperature generally is from about 40°C to about 80°C, when azo dicyanodivaleπc acid is utilized, the temperature generally is from about 50°C to about 90°C, when di-t- butylperoxide is utilized, the temperature generally is from about 1 1 0°C to about 1 60°C, when s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) is utilized, the temperature is generally from about 80°C to about 200°C. The low polydispersity polymers prepared as stated above by the free radical polymerization can contain reactive end groups from the monomers which are able to undergo further chemical transformation or reaction Such as being joined with another polymer chain, such as to form block copolymers for example. Therefore, any of the above listed monomers, i.e. conjugated dienes or vinyl containing monomers, can be utilized to form block copolymers utilizing the s,s'-bιs-(α, α' - distributed - α" - acetic acid) - trithiocarbonate compounds as chain transfer agent Alternatively, the substituents may be non-reactive such as alkoxy, alkyl, or aryl Reactive groups should be chosen such that there is no adverse reaction with the chain transfer agents under the conditions of the experiment The process of this invention can be carried out in emulsion, solution or suspension in either a batch, semi-batch, continuous, or feed mode Otherwise-conventional procedures can be used to produce narrow polydispersity polymers For lowest polydispersity polymers, the chain transfer agent is added before polymerization is commenced For example, when carried out in batch mode in solution, the reactor is typically charged with chain transfer agent and monomer or medium plus monomer. The desired amount of initiator is then added to the mixture and the mixture is heated for a time which is dictated by the desired conversion and molecular weight. Polymers with broad, yet controlled, polydispersity or with multimodal molecular weight distribution can be produced by controlled addition of the chain transfer agent over the course of the polymerization process. In tne case of emulsion or suspension polymerization the medium will often be predominately water and the conventional stabilizers, dispersants and other additives can be present. For solution polymerization, the reaction medium can be chosen from a wide range of media to suit the monomer(s) being used. As already stated, the use of feed polymerization conditions allows the use of chain transfer agents with lower transfer constants and allows the synthesis of block polymers that are not readily achieved using batch polymerization processes. If the polymerization is carried out as a feed system the reaction can be carried out as follows. The reactor is charged with the chosen medium, the chain transfer agent and optionally a portion of the monomer(s) . The remaining monomer(s) is placed into a separate vessel. Initiator is dissolved or suspended in the reaction medium in another separate vessel. The medium in the reactor is heated and stirred while the monomer + medium and initiator + medium are introduced over time, for example by a syringe pump or other pumping device The rate and duration of feed is determined largely by the quantity of solution the desired monomer/chain transfer agent/initiator ratio and the rate of the polymerization. When the feed is complete, heating can be continued for an additional period. Following completion of the polymerization, the polymer can be isolated by stripping off the medium and uπreacted monomer(s) or by precipitation with a non-solvent Alternatively, the polymer solution/emulsion can be used as such, if appropriate to its application. The invention has wide applicability in the field of free radical polymerization and can be used to produce polymers and compositions for coatings, including clear coats and base coat finishes for paints for automobiles and other vehicles or maintenance finished for a wide variety of substrates Such coatings can further include pigments, durability agents, corrosion and oxidation inhibitors, rheology control agents, metallic flakes and other additives. Block and star, and branched polymers can be used as compatibihsers, thermoplastic elastomers, dispersing agents or rheology control agents. Additional applications for polymers of the invention are in the fields of imaging, electronics (e.g., photoresists) , engineering plastics, adhesives, sealants, and polymers in general. As can be seen in the above shown polymerization mechanism, the s,s'-bιs-( , α' - disubstituted - α" - acetic acid) - trithiocarbonate compound can be utilized to create telechelic polymers having two functional groups at both chain ends. The term "telechelic polymer" was proposed in 1 960 by Uraneck et al. to designate relatively low molecular weight macromolecules possessing one or more, and preferably two reactive functional groups, situated at the chain ends, thereof. The functional end groups of both the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound and the polymers formed therefrom, have the capacity for selective reaction to form bonds with another molecule. The functionality of a telechelic polymer or prepolymer is equal to the number of such end groups Telechelic polymers containing a functional group, such as COOH, at each end are useful for synthesizing further chain extended copolymers and block copolymers. The interest in telechelic polymers resides in the fact that such polymers can be used, generally together with suitable linking agents, to carry out three important operations: ( 1 ) chain extension of short chains to long ones by means of bifunctional linking agents, (2) formation of networks by use of multifunctional linking agents, and (3) formation of (poly)block copolymers by combination of telechelics with different backbones These concepts are of great industrial importance since they form the basis of the so-called "liquid polymer" technology exemplified by the "reaction injection molding" (RIM) . Great interest has aiso been shown by the rubber industry because the formation of a rubber is based on network formation. In classical rubber technology, this is achieved by the cross-linking of long chains that show high viscosity. The classical rubber technology, therefore, requires an energy-intensive mixing operation. The use of liquid precursors, which can be end-linked to the desired network, offers not only processing advantages, but in some cases, also better properties of the end- product. Further information about telechelic polymers and synthesis thereof can be found in "Telechelic Polymers: Synthesis and Applications" by Eric J. Goethe, CRC Press, Boca Raton, Florida, 1 989. The reaction conditions for the reactive functional acid end groups of the telechelic polymers or s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds of the present invention are generally the same as those for forming the above noted free radical polymers. The acid in the monomeric or in the polymeric form can be transformed to its derivatives in the conventional manner. For example, the ester can be made by refluxing the acid in alcohol with an acid catalyst with removal of water Amides can be formed by heating the acid with an amine with the removal of water. 2-hydroxy-ethyl ester can be formed by directly reacting the acid with an epoxide with or without a catalyst such as tπpheπylphosphine or an acid like toluene- sulfonic acid. As seen by the examples below, any of the above noted monomers such as the one or more diene monomers or one or more vinyl containing monomers, can be utilized to form the telechelic monomers from the bιs-(α, α' - distributed - " - acetic acid) - trithiocarbonate compounds of the present invention. Any of the above noted components, such as solvent, etc., can be utilized in the herein above stated amounts. The acid groups of the s,s'-bis-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound can be converted to other functional groups either before or after polymerization. Even if the s,s'- bis-(cc, cc' - disubstituted - α" - acetic acid) - trithiocarbonate compounds have functional end groups which have been converted from the acid end groups Defore polymerization, the monomers added during polymerization stili add to the chain between the sulfur-tertiary carbon as shown in the mechanisms above as well as below at XXIII and XXIV. The carboxy c end groups of the s,s'-bis-(α, α' - disubstituted - " - acetic acid) - trithiocarbonate compounds or the polymerized s,s'-bis-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds can be converted or changed into other functional end groups such as esters, thioesters, amides, beta mercapto esters, beta hydroxy esters, or beta ammo esters. Examples of these functional end groups are shown below. An example reaction forming a telechelic polymer from the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds of the invention when using a vinyl monomer is as follows: XXIII HOOC Of course, it is to be understood as indicated above, that the repeat units m and n can be derived either from conjugated diene monomers, or the indicated vinyl monomers, or combinations thereof, as generally set forth in formula W. Subsequently, other functional end groups can be derived from the acid groups of the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - tπthiocarbonate compound and can generally be represented by the formula: Q R 1 R 1 0 XXV E — C — C — S — C — S — C — C- R 2 R^ where E is set forth below. For example, R 1 R 1 XXVI HOOC - C- S- C- S- C- COOH + 2R'XH R' R 1 R 1 XXVII R'XOC - C - S — C -S -C -COXR' + 2H,0 R 2 R 2 (C) wherein E is XR', that is R' , independently, comprises H , C, - C 1 8 alkyls which can be optionally substituted with one or more halogen, hydroxyl, or alkoxy, C, - C, 8 hydroxyalkyls, and C, - C 18 aminoalkyls and X comprises oxygen, sulfur, NH, or NR' . The following is still another example of functional end groups which can be derived from the acid: R 1 S R 1 XXVIII I II I HOOC -C - S -C - S - C- COOH I I R 2 R 2 R 8 R 6 R 1 S R 1 R 6 R 8 XXIX HY - C - COOC - C- S- C - S — C — COO — C — C — YH R 9 R 7 R 2 R 2 R 7 R 9 wherein E is R 6 R 8 XXX I I O -C — C — YH R 7 R 9 that is where R 6 through R 9 , independently comprise H, λ - C 18 alkyls, aryl groups or substituted aryl groups having from 1 to 6 substituents on the ring, such as halogen, hydroxyl, or alkoxy, C, - C 18 hydroxyalkys, C - C 18 aminoalkyls, C, - C 18 mercapto alkyls, and the like. Y can comprise oxygen, sulfur, NH, or NR 6 to R 9 . A further example of still other functional end groups which can be derived from the acid groups of the s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compounds is as follows: R 1 S R 1 XXXI HOOC - C- S- C- S- C- COOH + 2R l ϋ Z base I I R 2 R 2 R 1 R 1 XXXII R 10 OOC — C - S - C- S - C - COOR 10 I I R 2 R 2 wherein E is OR 10 , that is where Z can comprise a leaving group, such as a ha de or alkylsulfonate or aryl sulfonate. R 10 can comprise C, - C 18 , a alkyl or substituted alkyl wherein said substituent is halogen, hydroxyl, or alkoxy, C, - C 18 hydroxyalkyl or C, - C 18 ammo alkyl and the like Preparation of the above shown methylesters of s,s'-bιs-(2- methyl-2-propanoιc acid) - trithiocarbonate is as follows: s,s'-bιs-(2- methyl-2-propanoιc acid) trithiocarbonate (R 1 ,R 2 = CH 3 ) (2.82g, 0.01 mole), Sodium carbonate powders (3.1 8g, 0.03 mole) and 1 5 ml dimethyl formamide were stirred under nitrogen at 40°C while a solution of methylioαide (3 41 g, 0.024 mole) in 2 ml dimethylformamide was added dropwise over 1 0 minutes. The reaction was stirred at 40-50°C for 2 hours, poured into 25 ml H 2 0 and extracted 3 times with a total of 200 ml. ether. The etherate solution was dried over magnesium sulfate and concentrated. The yellow solid was further purified by recrystal zation from hexanes Infrared and H'NMR showed the above desired product. An example of an already formed telechelic polymer, made from a vinyl monomer, undergoing conversion of the acid end group is as follows: HOOC - XXXIV HY- H where m and n are as set forth above. The above structure (XXXIV) was formed by reaction of epoxide with s,s'-bιs-(2-methyl-2-propanoιc acid) - trithiocarbonate (l) (R\R 2 = CH 3 , 0.01 mole) of the present invention and Epon ® Resin 828 (Shell chemicals, reaction product of bisphenol A and epichlorohydrin, 80-85 % diglycidyl ethers of bisphenol A) (70g) and trephenyl phosphine (0. 1 2g) were heated to 95°C under nitrogen. The reaction was monitored for the disappearance of the carboxyiic acid by titration. It was found the reaction was essentially complete in 1 .5 hours. The product structure can be further confirmed by mass spectroscopy. Another aspect of present invention further relates to forming the following compounds: ' R 1 R SH + CS- + CHCI, + 0=C + 4Na0H Q-X XXXV [phase transfer catalyst] ^ R 2 R ' R 1 1 - C -S — C — COO Na " + 3NaCI + 3H 2 0 XXXVI HCI R 1 1 - S — C - S — C - COOH + NaCI XXXVII R 2 wherein R 1 1 comprises a benzyl group, C, - C 18 alkyl, or substituted alkyl such as halogen, hydroxyl, or alkoxy, C η - C 18 hydroxyalkyl, carboxylalkyl, or carboalkoxyalkyl. Q + X is a phase transfer catalyst such as tetrabutylammoniumhydrogensulfate, or octadecyltπmethyiammoniumchloπde (Aliquot 336). The resulting compound is an s - substituted alkyl - s'- (α,α' - disubstituted - " - acetic acid) - trithiocarbonate. R 1 1 is an alkyl having from 1 - 1 8 carbon atoms, aralkyl, hydroxyalkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, or carboalkoxyalkyl, mercaptoalkyl, etc. R 1 and R 2 are as stated herein above. When s - substituted alkyl - s'- (α,α' - disubstituted - α" - acetic acid) - trithiocarbonate is employed either as an mifertor, or as a chain-transfer cgent, unless R ' is carboxyl alkyl, only one end of the polymer has a carboxyl function, i.e it is no longer a telechelic polymer. While various polymers have been set forth herein above, it is to be understood thai any of the carboxyl terminated polymers, such as W, or the E terminated polymers, and the like, can be reacted with one or more monomers and/or one or more polymers know to the art and to the literature to yield various resulting block polymers which are derived from the same monomer or from two or more different monomers. For example, each acid end group can be reacted with an excess of an epoxy compound such as a glycidyl bisphenol A and then subsequently polymerized with additional glycidyl bisphenol A to form an epoxy polymer Naturally, other block polymers or copolymers can be reacted with the carboxyiic end group or the other end groups generally denoted by E herein above. The present invention will be better understood by reference to the following examples which serve to describe, but not to limit, the present invention. EXAMPLES EXAMPLE 1 Synthesis of s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate, (R 1 = R 2 = CH,) 2CS, + CHCL + 0 + BuNHSO, 50%NaOH H + H,C CH, toluene Procedure: In a 500 ml jacketed flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and an addition funnel added 22.9 grams of carbon disulfide, 2.0 gram of tetrabutylammonium bisulfate and 1 00 ml toluene. The solution was stirred at 20°C under nitrogen and 1 68 grams of 50% sodium hydroxide solution was added dropwise to keep the temperature between 20-30°C. 30 mm. after the addition, a solution of 43.6 grams of acetone and 89.6 grams of chloroform was added at 20-30°C. The reaction was then stirred at I5-20°C overnight. 500 ml water was added to the mixture, the layers were separated. The organic layer was discarded and the aqueous layer was acidified with concentrated HCI to precipitate the product as yellow solid. 50 ml toluene was added to stir with the mixture. Filtered and rinsed the solid with toluene to collect 22.5 grams of product after drying in the air to constant weight. EXAMPLE 2 Synthesis of s,s'-bιs-(α, ' - disubstituted - α" - acetic acid) - trithiocarbonates. (R 1 = R 2 = CH 3 ) CH 3 S CH 3 0 50% NaOH H + CS 2 + CHCI 3 + Λ + Bu 4 NHS0 4 ► →* HOOC-t- S -C- S- COOH Mineral spirits CH 3 CH 3 CH 3 CH The procedure was essentially the same as in example 1 , except that mineral spirits replaced toluene as solvent. 40.3 grams of product was obtained as yellow solid. EXAMPLE 3 Synthesis of s-alkyl-s -(-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonates C 12 H 25 SH + CS 2 - CHCI 3 + (CH 3 ) 2 CO + R 4 N "CP NaOH H " ► S H 3 C 12 H 25 S- C — S^ COOH I CH 3 Procedure: Dodecylmerr-aptan (0 1 moie), and Aliquot 336 (0.004 mole) was dissolved in 48g acetone. 50% sodium hydroxide solution (0. 1 05 mole) was added, followed by dropwise addition of carbon disufide (0-1 mole) in 1 0g acetone solution. The media turned from colorless to yellow. After 20 mm., chloroform (0.1 5 mole) was added followed by dropwise addition of 50% NaOH (0.5 mole) and 5 g NaOH beads. The rxn was stirred at 1 5-20 ° C overnight, filtered and the sol. was rinsed with acetone The acetone layer was concentrated to dryness. The mass was dissolved in water, acidified with concentrated HCI to precipitate the product, rinsed with water to collect the yellow solid. The solid was dissolved in 350 ml hexanes. The solution was dried over magnesium sulfate and filtered. The organic solution was cooled to precipitate the product as yellow flakes. Yield is 85% . EXAMPLE 4 Polymerization of Prior Art Compounds S ^ ^ COOC 8 H 7 CH, S^ S - CH, (°> + AIBN 52°C polyacrylate acetone Procedure: Dibenzyltrithiocarbonate ( 1 .54 g, 5.3 mmole), 2-ethylhexylacrylate (25grams 1 35.7 mmole), AIBN (0.05g, 0.3mmole) and acetone (25ml) were mixed. 1 ml of undccane was added as GC internal standard for calculating the conversion. The solution was purged with nitrogen for 1 5 m . before heating to 52°C under nitrogen. No exotherm was detected throughout the reaction. Aliquots of the sample were taken for GC and GPA analyses during the course of the polymerization. The following table showed the progress of the polymerization in 7 hours. EXAMPLE 5 Polymerization with s,s'-bis-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonates CH 3 i CH 2 52°C COOC 8 H 17 + HOOC^ — S S -j — COOH + AIBN ► polyacrylate CH 3 CH 3 acetone Procedure: Following the same procedure as in example 4, the novel tricarbonate ( 1 .50g, 5.3mmole) , 2- ethylhexylacrylate (25g, 1 35.7 mmole) , AIBN (0.05g, 0.3mmole) and acetone (25ml) were mixed. 1 ml of undecane was added as internal standard The reaction was stirred at 52°C for 7 hours. The following table showed the conversion and the molecular weights of the resulting polymer. EXAMPLE 6 Polymerization with s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) trithiocarbonates. CH 3 CH, 60°C COOC 8 H 17 + HOOC- - S S-f- COOH + AIBN 'polyacrylate CH 3 CH 3 Procedure: This is a bulk polymerization with the trithiocarbonate as chain-transfer agent The trithiocarbonate ( 1 .0g, 3.5mmole), 2-ethylhexylacrylate (25g, 1 35.7mmole), AIBN (0.05g, 0.3mmole) and 1 ml undecane (internal standard) were purged with nitrogen, then heated to 60°C for 3 hours. The following table showed the conversion and the molecular weight of the polymer. EXAMPLE 7 Polymerization with s,s'-bis-(α, α' - disubstituted - α" - acetic acid) trithiocarbonates. CH 3 CH 1 30°C polyacrylate C0 2 Bu + HOOC + S S + COOH CH- CH, Procedure: The trithiocarbonate was used as inifertor. Trithiocarbonate ( 1 .0g, 3.5 mmole), n-butylacrylate (20g, 1 56.1 mmole) with 1 ml decane as internal standard were purged with nitrogen for 1 5 min., then polymerized at 1 30°C under nitrogen for 6 hours. The following table showed the conversion and the molecular weights of the polymer. EXAMPLE 8 Free Radical Polymerization utilizing s,s'-bis-(α, α' - disubstituted - α" acetic acid) - trithiocarbonates as inifertor. CO, -CH, OOH 1 75°C polyacrylate ► Procedure: The trithiocarbonate (2.0g, 7.1 mmole) and 2-ethylhexylacrylate (25. Og, 1 35.7mmole) were purged with nitrogen for 1 5 min then heated to 1 75°C for 1 0 hours. The following table showed the conversion and molecular weighs of the polymer. EXAMPLE 9 Polymerization with s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) trithiocarbonates. PhCH polystyrene Procedure: The trithiocarbonate was used as inifertor to make polystyrene. The trithiocarbonate (2.0g, 7.1 mmole) and styrene (25g, 240.4mmole) with 1 ml decane as internal standard were polymerized at 1 40°C under nitrogen for 6 hours. The following table showed the progress of the polymerization. EXAMPLE 10 Polymerization with s,s'-bis-(α, α' - disubstituted - α" - acetic acid) trithiocarbonates. COOC 8 H 17 + polyacrylate CH, CH, Styrene polyacrylate - b - polystyrene 60 σ C copolymer Procedure: The trithiocarbonate was used as chain-transfer agent to make block copolymers of 2-ethylhexylacrylate and styrene. The trithiocarbonate ( 1 .5g , 5.3mmole) , 2-ethylhexylacrylate (30g, 1 62.8mmole) and AIBN (0.03g, 0. 1 δmmole) with 1 ml undecane as the internal standard were polymerized at 60°C under nitrogen as before. 6.5 hours later, styrene ( 1 5g, 1 44.2mmole) and AIBN (0.03g, 0.1 8mmole) was added . The polymerization continued and the following shows the progress. Styrene added EXAMPLE 1 1 Polymerization with the trithiocarbonate from example 3. The trithiocarbonate ( 1 .82g. δmmole) , n-butyl acrylate (25g, 1 95. 1 mmole) and AIBN (0.04g, 0.25mmole) with 1 ml undecane as the internal standard were polymerized under nitrogen atmosphere for 7 hours. It showed 97.5% conversion by GC as depicted in the following table: While in accordance with the patent statutes the best mode and preferred embodiment have been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims.

Claims: CLAIMS What is claimed is: 1 . A compound having the formula R 1 S R 1 I II I HOOC — C — S — C— S — C — COOH I I R 2 R 2 wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; where said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof, or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms. 2. The compound of claim 1 , wherein R 1 and R 2 are, independently, said alkyl, or said substituted alkyl having one or more substituents, or said one or more aryls, or said substituted aryl having one or more substituents, or combinations thereof. 3. The compound of claim 1 , wherein R 1 and R 2 are, independently, methyl or phenyl. 4. A polymerization initiator, comprising: the compound of claim 1 . 5. A polymerization initiator, comprising: the compound of claim 2. 6. A free radical polymerization initiator, comprising: the compound of claim 3. 7. A polymerization chain transfer agent, comprising: the compound of claim 1 . 8. A polymerization chain transfer agent, comprising: the compound of claim 2. 9. A free radical polymerization chain transfer agent, comprising: the compound of claim 3 1 0 A polymerization inifertor, comprising the compound of claim 1 1 1 . A polymerisation inifertor, compπsing- the compound of claim 2 1 2 A free radical polymerization inifertor, comprising: the compound of claim 3. 1 3 A polymerization chain terminator, comprising: the compound of claim 1 . 4. A method for forming an s,s'-bιs-(α, a' - disubstituted - α" - acetic acid) - tπthiocarbonate compound, comprising the steps of: reacting carbon disulfide and a base to form an intermediate tπthio structure; reacting said tπthio intermediate with a 1 -dιsubstιtuted-2- dihaloepoxide, or with the reaction product of a haloform and a ketone in the presence of said base, to form a dicarboxylated salt, and acidifying said dicarboxylated salt to form said s,s'- bιs-(α, α' - disubstituted - " - acetic acid) - trithiocarbonate. 5. A method according to claim 1 4, wherein said reaction temperature is from about minus 1 5°C to about 80°C. 6 A method according to claim 1 5 , wherein said haloform is chloroform or bromoform or a blend thereof, and wherein said ketone has the formula 0 R 1 - C— R' wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or moi e substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms. 1 7. A method according to claim 1 6, including a catalyst. 1 8. A method according to claim 1 7, wherein said s,s'-bιs-( , ' - disubstituted - α" - acetic acid) - trithiocarbonate has the formula: R 1 S R 1 I II I HOOC — C — S — C — S — C — COOH I I R 2 R 2 wherein R 1 and R 2 , independently, is said R 1 and said R 2 of said ketone. 1 9. A method according to claim 1 8, wherein said catalyst is present in an amount of from about 0 1 to about 1 0 mole percent per mole of said carbon disulfide 20. A method according to claim 1 9, wherein said haloform is present in an amount from about 1 1 0 mole percent to about 2,000 mole percent per mole molecule of said carbon disulfide, and wherein said ketone is present in an amount from about 1 1 0 mole percent to about 2,000 mole percent per moie of said carbon disulfide. 21 . A method according to claim 20, wherein said R 1 and R 2 , independently, are methyl or phenyl groups, and wherein said haloform is chloroform. 22. A method according to claim 21 , wherein the amount of said base is from about 5 moles to about 1 5 moles per mole of said carbon disulfide. 23. A method according to claim 22, wherein said catalyst is a polyether, or an onium salt, or combinations thereof. 24. A polymer, comprising: repeat units derived from the free radical polymerization of at least one vinyl containing monomer, or at least one conjugated diene monomer, or combinations thereof, in the presence of a s,s'-bιs- (α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound having the formula: R 1 S R 1 I II I HOOC — C S — C — S — C — COOH R 2 R 2 or a functional derivative of said end group thereof wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms. 5. A polymer according to claim 24, wherein said conjugated diene monomer has from 4 to 1 2 carbon atoms, and wherein said vinyl containing monomer has the formula: where R 3 comprises hydrogen, halogen, C-, - C 4 alkyl, or substituted C, - C 4 alkyl wherein said substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR 5 ), carboxy, acyloxy, aroyloxy(0 2 CR 5 ), alkoxy-carbonyl(C0 2 R 5 ), or aryloxy- carbonyl; wherein R Λ comprises hydrogen, R 5 , C0 2 H, C0 2 R 5 , COR 5 , CN, CONH 2 , CONHR 5 , 0 2 CR 5 , OR 5 or halogen; and wherein R 5 comprises C, - C 18 alkyl, substituted C, - C 18 alkyl , C, - C 18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, and wherein said substituents, independently, comprise one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy, (and salts) , sulfonic acid (and salts) , alkoxy- or aryloxy-carbonyl, sicyanato, cyano, silyl, halo or dialkylamino. A polymer according to claim 25, wherein said one or more monomers is an acrylate having from 1 to 8 carbon atoms, a methacrylate having form 1 to 8 carbon atoms, styrene, butadiene, isoprene, acrylonitrile, or combinations thereof, and wherein R 1 and R 2 , independently, are methyl or phenyl. A polymer according to claim 24, wherein said s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate is an initiator, or a chain transfer agent, or both. A polymer according to claim 25, wherein said s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate is an initiator, a chain transfer agent, or both. A polymer according to claim 26, wherein said s,s'-bιs-(α, ' - disubstituted - α" - acetic acid) - trithiocarbonate is an initiator, a chain transfer agent, or both. A polymer according to claim 27, including a free radical initiator. A polymer according to claim 28, including a free radical initiator. A polymer according to claim 29, including a free radical initiator A polymer according to claim 30, wherein said free radical initiator is 2,2 '-azobιs(ιsobutyroπιtπle)(AIBN) , or 4,4'-azobιs(4- cyanopeπtanoic acid) , 2,2'-azobιs(2-cyano-2-butane); or 1 , 1 '- azobιs(cyciohexanecarbanιtπle), or combinations thereof. A polymer according to claim 31 , wherein said free radical initiator is 2,2'-azobιs(ιsobutyronιtπle) (AIBN); or 4,4'-azobιs(4- cyanopentanoic acid) , 2,2'-azobιs(2-cyaπo-2-butane); or 1 , 1 '- azobιs(cyclohexanecarbanιtπle); or combinations thereof, and wherein the amount of free radical initiator is from about 0.01 to about 25 mole percent based upon the total number of moles of said s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound. 35. A polymer according to claim 32, wherein said free radical initiator is 2,2'- azobιs(ιsobutyronιtπie) (AIBN); or 4,4'-azobιs(4-cyanopentaπoιc acid); 2,2'-azobιs(2-cyano-2-butane) ; or 1 , 1 '- azobιs(cyclohexanecarbanιtrile); or combinations thereof, and wherein the amount of free radical initiator is from about 0.1 to about 1 0 mole percent based upon the total number of moles of said s,s'-bιs-(α, α' - disubstituted - α" - acetic acid) - trithiocarbonate compound. 36. A polymer according to claim 27, wherein the polydispersity of said polymer is 1 .75 or less. 37. A polymer according to claim 28, wherein the polydispersity of said polymer is 1 .75 or less. 38 A polymer according to claim 29, wherein the polydispersity of said polymer is 1 .50 or less. 39. A polymer according to claim 24, wherein the polydispersity of said polymer is 1 .50 or less. 40. A compound having the formula: O R 1 S R 1 O II I II I II E — C — C — S — C — S — C — C- E wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl πng; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms; and wherein E is XR', where R', independently, comprises H, C, - C 18 alkyl, a substituted C, - C 18 alkyl wherein said substituent is halogen, hydroxyl, or alkoxy, a C, - C 18 hydroxyalkyl, or a C, - C 18 aminoalkyl, and X comprises oxygen, sulfur, NH, or NR; or wherein E is R 5 R s O - C — C — YH I I R ^ R 9 wherein R 5 through R 9 , independently, comprise H, C, - C 18 alkyl, aryl, or a substituted aryl having from 1 to 6 substituents on the ring wherein said substituent is halogen, hydroxyl, or alkoxy, C, - C ι a hydroxy alkyl, C, - C 18 ammo alkyl, C, - C 1 8 or mercapto alkyl, and wherein Y comprises oxygen, sulfur, NH, or NR 6 to R 9 ; or wherein, E is OR 10 where R 10 comprises an alkyl containing from 1 to 1 8 carbon atoms, or a substituted alkyl containing from 1 to 1 8 carbon atoms wherein said substituent is halogen, hydroxyl, or alkoxy, or a hydroxy alkyl having from 1 to 1 8 carbon atoms, or an am o alkyl having from 1 to 1 8 carbon atoms, or combinations thereof; or combinations thereof. 41 . The compound of claim 40, wherein R 1 and R 2 are, independently, said alkyl, or said substituted alkyl having one or more substituents, or said one or more aryls, or said substituted aryl having one or more substituents, or combinations thereof. 42. The compound of claim 41 , wherein R 1 and R 2 are, independently, methyl or phenyl. 43. A polymerization initiator, comprising the compound of claim 40. 44 A polymerization initiator, comprising the compound of claim 42. 45. A free radical initiator, or a chain transfer agent, or both, comprising the compound of claim 40 46. A free radical initiator, or a chain transfer agent, or both, comprising the compound of claim 42 47 A composition comprising: a polymer having the formula HOOC COOH where R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms; and wherein said repeat group is derived from said at least one conjugated diene monomer has a total of from 4 to 1 2 carbon atoms, and wherein said at least one vinyl containing monomer has the repeat unit R ; -H 2 C - C wherein R 3 comprises hydrogen, halogen, C, - C 4 alkyl, or substituted C, - C 4 alkyl wherein said substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR 5 ) , carboxy, acyloxy, aroyloxy(0 2 CR 5 ) , alkoxy-carbonyl(C0 2 R 5 ), or aryloxy- carbonyl; wherem R 4 comprises hydrogen, R 5 , C0 2 H, C0 2 R 5 , COR 5 , CN, CONH 2 , CONHR 5 , 0 2 CR 5 , OR 5 or halogen; and wherein, R 5 comprises C, - C 18 alkyl, substituted Ci - C 18 alkyl, C 2 - C 18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, and wherein said substituents, independently, comprise one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy, (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, sicyanato, cyano, silyl, halo or dialkylamino, and wherein m and n, independently, is from about 1 to about 1 0,000. 48 A composition according to claim 47, wherein R 1 and R 2 , independently, are said alkyl, or said substituted alkyl having one or more substituents, or said one or more aryls, or said substituted aryl having one or more substituents, or combinations thereof. 49 A composition according to claim 48, wherein R 1 and R 2 , is independently, methyl or phenyl, and wherein m is from about 5 to about 500, and n is from about 5 to about 500 50. A composition according to claim 49, wherein said m repeat group and said n repeat group is derived, independently, from said one or more monomers which is an acrylate having from 1 to 8 carbon atoms, a methacrylate having from 1 to 8 carbon atoms, styrene, butadiene, isoprene, or acrylonitrile, or combinations thereof, and wherein m is from about 1 0 to about 200, and wherein π is from about 1 0 to about 200 5 1 . A composition according to claim 47, wherein the polydispersity of said polymer is 1 .75 or less. 52. A composition according to claim 48, wherein the polydispersity of said polymer is 1 75 or less. 53. A composition according to claim 49, wherein the polydispersity of said polymer is 1 .50 or less. 54. A composition according to claim 50, wherein the polydispersity of said polymer is 1 .50 or less. 55 A composition comprising a polymer having the formula R 1 O II C- E R 2 e ereof/ where R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms; and wherein said repeat group is derived from said at least one conjugated diene monomer has a total of from 4 to 1 2 carbon atoms, and wherein said at least one vinyl containing monomer has the repeat unit R 3 -H 2 C - C R 4 wherein R 3 comprises hydrogen, halogen, C, - C 4 alkyl, or substituted C, - C alkyl wherein said substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR 5 ) , carboxy, acyloxy, aroyloxy(0 2 CR 5 ) , alkoxy-carbonyl(C0 2 R 5 ) , or aryloxy- carbonvl; wherein R 4 comprises hydrogen, R 5 , C0 2 H, C0 2 R 5 , COR 5 , CN, CONH 2 , CONHR 5 , 0,CR 5 , OR 5 or halogen, and wherein, R 5 comprises C, - C 18 alkyl, substituted C, - C 18 alkyl, C 2 - C 18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, and wherein said substituents, independently, comprise one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy, (and salts) , sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, sicyanato, cyano, silyl, halo or dialkylamiπo, and wherein m and n, independently, is from about 1 to about 10,000, and wherein E is XR', where R', independently, comprises H, C, - C 1S alkyl, a substituted C, - C 18 alkyl wherein said substituent is halogen, hydroxyl, or alkoxy. C, - C 18 hydroxyalkyl, or a C, - C, 8 ammoalkyl, and X comprises oxygen, sulfur, NH, or NR; or wherein E is R 6 R 8 O -C — C— YH R 7 R 9 wherein R 6 through R 9 , independently, comprise H, C 1 - C 18 alkyl, aryl, or a substituted aryl having from 1 to 6 substituents on the ring wherein said substituent is halogen, hydroxyl, or alkoxy , Ci - C 18 hydroxy alkyl, C, - C 18 ammo alkyl, C, - C 18 or mercapto alkyl, and wherein Y compπses oxygen, sulfur, NH, or NR 6 to R 9 ; or wherein, E is OR' c where R 10 comprises an alkyl containing from 1 to 18 carbon atoms, or a substituted alkyl containing from 1 to 18 carbon atoms wherein said substituent is halogen, hydroxyl, or alkoxy, or a hydroxy alkyl having from 1 to 18 carbon atoms, or an ammo alkyl having from 1 to 18 carbon atoms, or combinations thereof, or combinations thereof. 56. A composition according to claim 55, wherein R 1 and R 2 , independently, are said alkyl, or said substituted alkyl having one or more substituents, or said one or more aryls, or said substituted aryl having one or more substituents, or combinations thereof. 57. A composition according to claim 56, wherein R 1 and R 2 , are independently, methyl or phenyl, and wherein m is from about 5 to about 500, and n is from about 5 to about 500. 58. A composition according to claim 56, wherein R 3 said m repeat group and said n repeat group is derived, independently, from said one or more monomers which is an acrylate having from 1 to 8 carbon atoms, a methacrylate having from 1 to 8 carbon atoms, styrene, butadiene, isoprene, or acrylonitrile, or combinations thereof, and wherein m is from about 1 0 to about 200, and wherein n is from about 1 0 to about 200 59. A composition according to claim 55, wherein the polydispersity of said polymer is 1 75 or less 60. A composition according to claim 56, wherein the polydispersity of said polymer is 1 75 or less. 61 A composition according to claim 57, wherein the polydispersity of said polymer is 1 .50 or less. 62. A composition according to claim 58, wherein the polydispersity of said polymer is 1 .50 or less. 3. A composition comprising a polymer having the formula: S R 1 1 I R 1 1 — S — C - S — C - COOH I R 2 wherein R 1 1 is benzyl, a C, through C 18 alkyl, or a substituted C, to C 18 alkyl wherein said substituted group is one or more halogen, hydroxyl, or alkoxy, or a C-, to C 1 8 hydroxyalkyl, or a C T to C 18 alkyl carboxyl, or a C^ to C 18 alkylcarboalkoxy, and wherein R 1 and R 2 , independently, is an alkyl having from 1 to about 6 carbon atoms, or a substituted C, to about C 6 alkyl having one or more substituents, or one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring; wherein said one or more substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or combinations thereof; or wherein R 1 and R 2 are part of a cyclic ring having from about 5 to about 1 2 total carbon atoms.

Inventors: LAI JOHN T, LAI, JOHN, T.
Applicants: GOODRICH CO B F, THE B.F.GOODRICH COMPANY
Application year: 2001
Main classification: C07C329
IPC codes: C07B61, C07C329, C07C333, C08F2, C08F4, C08F20, C08G75