FIELD OF THE INVENTION [0001] The present invention relates to thiocarbonate compounds which are curable and include at least one polymerizable functional group, preferably one or more unsaturated groups. Curable compositions including the curable polymerizable group containing thiocarbonate compounds are disclosed. In one embodiment, the curable compositions comprise the curable polymerizable group containing thiocarbonate compounds and a reactive diluent, or a photoinitiator, or a combination thereof. Methods for preparing the curable thiocarbonate compounds, compositions containing the thiocarbonate compounds, and cured compositions are also described. Curing mechanisms include, but are not limited to, radiation, thermal, cationic and oxidative curing. The curable thiocarbonate compounds are useful as coatings, adhesives, and sealants for various substrates such as wood, paper, plastic, metal, or the like.

BACKGROUND OF THE INVENTION [0002] Ultraviolet light (UV), electron beam, x-ray, peroxy, thermal, redox, or radiation curable oligomers or polymers having curable groups such as allyl, vinyl ether, or acrylate groups are known in the art. Examples of curable polymers include various acrylate terminated polyesters, polyethers, urethanes and polyacrylates. These oligomers or polymers have several disadvantages. With the chemistries currently available in the art, oligomers with terminal acrylate groups are not easy to prepare for polyacrylates and poly(acrylate/urethanes). Crosslinking sites at the terminal ends of a polymer are most desirable in order to retain the acrylate properties of the polymer. A second disadvantage is that the available curable oligomers or polymers do not have adequate performance for exterior applications in most cases. A further disadvantage is that the available curable oligomers or polymers exhibit viscosities which are typically too high for practical use and range from a few thousand to tens of thousands or even millions of centipoises. In order to reduce viscosity, reactive diluents have been added to the oligomers or polymers, but the additives generally increase the toxicity and/or odor of the formulations. Acrylic polymers have been known to offer superior exterior qualities, however most curable oligomers or polymers are not polyacrylate based.

SUMMARY OF THE INVENTION [0003] A plurality of curable thiocarbonate compounds are disclosed by the present invention. The thiocarbonates include at least one curable functional group such as an unsaturated group derived from an acid such as a (meth)acrylic, itaconic, fumaric, styrene sulfonic or maleic acid, an allyl group containing monomer, or a vinyl group containing monomer. The term (meth)acrylic acid when utilized herein includes both methacrylic and acrylic acid. Preferably the curable groups are located at chain ends. [0004] In one embodiment, a curable thiocarbonate is formed via an esterification reaction of a carboxylic acid group (or derivative) containing thiocarbonate with a hydroxyl group containing compound bearing a curable polymerizable functional group, such as a hydroxy alkyl (meth)acrylate or allyloxy ethanol. [0005] In another embodiment, curable thiocarbonate urethane compounds are prepared from the reaction of an isocyanate terminated thiocarbonate compound with a hydroxyl group containing compound bearing a curable group such as an acrylate, i.e., a hydroxy alkyl (meth)acrylate. [0006] In yet a further embodiment, the curable thiocarbonate compounds are derived from the reaction of a thiocarbonate compound having carboxylic acid, alcohol, or amino group(s), with an epoxy group containing compound bearing a curable functional group such as glycidyl (meth)acrylate. [0007] It is additionally possible in further embodiments to react a carboxylic acid group containing thiocarbonate compound with thionyl chloride and subsequently a hydroxyl group containing compound bearing a polymerizable functional group, resulting in a curable thiocarbonate compound. [0008] In another embodiment, a curable thiocarbonate compound is prepared by converting the acid group of a thiocarbonate compound to an alcohol, for example through esterification with a polyol such as a diol, and subsequently reacting the alcohol end group(s) with an acid or derivative, having a polymerizable group, such as any of the unsaturated acids mentioned in the "Summary of the Invention" above. [0009] In yet a further embodiment, a thiocarbonate compound one acid group is reacted with a carbodiimide such as cyanamide, bearing one or more a polymerizable functional groups. [0010] Another embodiment involves reacting an acid group containing thiocarbonate compound with an olefin containing amine bearing a polymerizable functional group wherein amidization of the acid group of the thiocarbonate compound is performed. [0011] Curable compositions including thiocarbonate compounds having at least one curable functional group are also described. In one embodiment, the curable compositions comprise thiocarbonate compounds having at least one curable functional group and one or more photoinitiators. It is desirable in some embodiments to include additional reactive diluents or monomers in the curable compositions comprising the curable thiocarbonate compound in order to modify properties of the uncured compositions and/or cured polymers and coatings resulting from the compositions. Examples of suitable additional diluents include curable oligomers, polymers, or resins such as (meth)acrylates which are mono-, di- or tri-functional, acrylated epoxy oligomers, (meth)acrylate-containing urethane oligomers, (meth)acrylate polyester oligomers, acrylated acrylic oligomers, acrylated esters of phosphoric acid, cycloaliphatic epoxide resins, silicone- containing (meth)acrylates and allylics, and the like. In some embodiments both reactive diluents and photoinitiators are present in the curable compositions including the thiocarbonate compounds having at least one radiation curable functional group. In yet another embodiment, the compositions comprise a thiol or polythiol compound which can be co-cured with the curable thiocarbonates, preferably utilizing UV radiation. [0012] This invention also includes a composition that contains an epoxy group for cationic radiation curing. For example, carboxyl-terminated thiocarbonyl compounds or a polymer made from them react with excess epoxide(s) which can be cationically cured with radiation in the presence of a conventional initiator such as a diaryliodonium or diarylsulfonium salt. UV-curable containing vinyl functional groups as mentioned in this invention can be mixed with the cationic curables and cured cationically. Epoxy, vinyl ether or vinyl containing polymers or thiocarbonyl compounds can be cured cationically with, for example, vinyl, epoxy or vinyl ether diluents. [0013] Several methods for forming curable thiocarbonate compounds are disclosed. Additionally, methods for forming compositions and cured coatings or articles formed from compositions including the curable thiocarbonates are also described.

DETAILED DESCRIPTION OF THE INVENTION [0014] The curable thiocarbonate compounds of the present invention can be formed from various thiocarbonate compounds by reaction with other compounds having at least one curable moiety. The thiocarbonate compounds are radiation curable and able to react and/or "cure" upon exposure to a radiation energy source, such as but not limited to, ultraviolet light (UV) or an electron beam, optionally in the presence of photoinitiator, which is generally a free-radical or cationic initiator. Compositions including the thiocarbonates can also be cured using thermal, cationic, oxidative or other mechanisms. [0015] Thiocarbonate Compounds The thiocarbonate compounds utilized in the present invention are preferably polythiocarbonates such as dithiocarbonate or trithiocarbonate compounds and derivatives thereof. By the term "thiocarbonate" it is meant a compound having at least one segment having the formula: S

— X-C- S^ wherein X comprises OR, SR, or NR2 for example with R being various hydrocarbon, heteroatom and/or hydrogen containing structures or the like preferably as illustrated hereinbelow, but not limited thereto. [0016] Suitable trithiocarbonate compounds for use in the present invention, but not limited thereto, are disclosed in U.S. Patent No. 6,596,899 to Lai, herein fully incorporated by reference. In one embodiment, trithiocarbonate compounds have the following general formula:

wherein R1 and R2, independently, is the same or different, and is a linear or branched alkyl having from 1 to about 6 carbon atoms, or a Ci to about Ce 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'-bis-2-methyl-2- propanoic acid-trithiocarbonate and s,s'-bis-(2-phenyl-2-propanoic acid)- trithiocarbonate. R1 and R2 can also form or be a part of a cyclic ring having from 5 to about 12 total carbon atoms. R1 and R2 are preferably, independently, methyl or phenyl groups. [0017] The abbreviated reaction formula for one method for the preparation of s,s'-bis-(α,α'-disubstituted-α"-acetic acid) - trithiocarbonates is generally written as follows: O R1 R1 1. NaOH 2CS9 + CHX-, + R1 -C-R2 HOOC-C-S-C-S-C-COOH 2. HCL R2 R2

[0018] The process utilized to form s,s'-bis-(α,α'-disubstituted-α"-acetic acid)- trithiocarbonate compounds is generally a multi-step process and includes combining the carbon disulfide and a base whereby an intermediate trithio structure is formed. Ketone can serve as solvent for the carbon 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-trihalomethyl-α- alkanol are added to the trithio intermediate mixture and reacted in the presence of additional base. The formed reaction product, is subsequently acidified, thus completing the reaction and forming the above described s,s'-bis-(α,α'- disubstituted-α"-acetic acid)-trithiocarbonate compound. [0019] Another aspect of present invention utilizes trithiocarbonate compounds having the following formula:

wherein R3 comprises a benzyl group, Ci - Ci8 alkyl, or substituted alkyl such as halogen, hydroxyl, or alkoxy, Ci - C-is hydroxyalkyl, aralkyl, hydroxyalkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl or mercaptoalkyl, and R1 and R2 are defined hereinabove. The resulting compound is an s-substituted- s'- (α,α'- disubstituted-α"-acetic acid)-trithiocarbonate. [0020] Dithiocarbonate compounds which are utilized in some embodiments of the present invention are disclosed in U.S. Application Serial No. 10/278,335 filed 10/23/02 and U.S. Application Serial No. 10/681 ,679 filed 10/8/03, herein fully incorporated by reference. In one embodiment the dithiocarbamate compounds have the following formula:

wherein j is 1 or 2, with the proviso that when j is 1 , T is — fNR R ); ancj wnen j is 2, T is a divalent radical having a nitrogen atom directly connected to each carbon atom of the two thiocarbonyl groups present; wherein R4 and R5, independently, is the same or different, is optionally substituted, and is a linear or branched alkyl having from 1 to about 6 or about 12 carbon atoms; or an aryl group having from 6 to about 18 carbon atoms, optionally containing heteroatoms; wherein the R4 and/or R5 substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms; an aryl group; a halogen; a cyano group; an ether having a total of from 2 to about 20 carbon atoms; a nitro; or combinations thereof. R4 and R5 can also form or be a part of a substituted or unsubstituted cyclic ring having from 3 to about 12 total carbon atoms wherein the substituents are described above. R4 and R5 are preferably, independently, methyl or phenyl groups; wherein R6 and R7, independently, is the same or different, optionally is substituted, optionally contains heteroatoms; and is hydrogen; a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl group having from about 6 to about 18 carbon atoms optionally saturated or unsaturated; an arylalkyl having from about 7 to about 18 carbon atoms; an alkenealkyl having from 3 to about 18 carbon atoms; or derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms. R6 and R7 can also be derived from amines such as, but not limited to, piperazine, morpholine, pyrrolidine, piperidine, 4-alkylamino- 2,2,6,6-tetramethyl piperidine, 1-alkylamioalkyl-3, 3, 5, 5-tetramethyl-2 piperazinone, hexamethyleneimine, phenothiazine, iminodibenzyl, phenoxazine, N,N'-diphenyl- 1,4-phenylenediamine, dicyclohexylamine and derivatives thereof. R6 and R7 can also form a substituted or unsubstituted cyclic ring, optionally containing heteroatoms, along with the nitrogen having a total of from 4 to about 12 carbon atoms, such as benzotriazole, tolyltriazole, imidazole, 2-oxazolidone, 4,4- dimethyloxazolidone and the like. The R6 and R7 substituents, independently, can be the same as described herein with respect to R13. R6 and R7 are preferably, independently, a phenyl group or an alkyl or substituted alkyl having from 1 to about 18 carbon atoms such as a methyl group, or R6 and R7, independently, are hexamethylene. [0021] When j is 1 , T of above formula is -(-NR R ) anc| tne dithiocarbamate compound is a S-(α,α'-disubstituted-α"-acetic acid) dithiocarbamate generally having the following formula:

wherein R4, R5, R6, and R7 are as defined hereinabove. [0022] When j is 2, the dithiocarbarbamate compound is a bis-S-(α,α'- disubstituted-α"-acetic acid) dithiocarbamate having the following formula:

HOOC ;-- — Q— COOH

wherein R4 and R5 are defined hereinabove; and wherein T is a divalent bridging radical having a nitrogen atom directly connected to each of the thiocarbonyl groups present. [0023] In one embodiment T is:

-( N)- ;

wherein R8 and R9, independently, is the same or different, is optionally substituted, and is hydrogen, a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl group having from about 6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18 carbon atoms, or an alkenealkyl having from 3 to about 18 carbon atoms, wherein the substitutents can be the same as described herein for R1 and R2; wherein R10 is optionally substituted, and is an alkylene group having from 1 to about 18 carbon atoms with about 1 to about 6 carbon atoms preferred, or derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2 or are heteroatoms such as oxygen, nitrogen, sulfur or phosphorous; p is 0 or 1 , and wherein R11 and R12 independently, is the same or different, and is optionally substituted as described for R1 and R2, and is an alkylene group having from 1 to about 4 carbon atoms, with R11 and R12 preferably having a collective total of 3 to 5 carbon atoms. [0024] In further embodiments, T is:

wherein n is 0 to about 18, with 0 to about 6 preferred;

wherein n is 0 to about 18, with 0 to about 6 preferred. [0025] Some specific non-limiting examples of T bridging radicals are:

(CH 2)n / / \ \ -(N N)- \ / \ / (CH 2/m

wherein n plus m is 3 to 5. [0026] The S-(α,α'-disubstituted-α"-acetic acid) or bis-S-(α,α'-disubstituted-α"- acetic acid) dithiocarbamates are generally a reaction product of a metal salt of a dithiocarbamate, a haloform, and a ketone. A phase transfer catalyst, solvent, and a base such as sodium hydroxide or potassium hydroxide can also be utilized to form the S-(α,α'-disubstituted-α"-acetic acid) or bis S-(α,α'-disubstituted-α"- acetic acid) dithiocarbamates. [0027] It is to be understood throughout the application formulae, reaction schemes, mechanisms, etc., and the specification that metals such as sodium or bases such as sodium hydroxide are referred to and the application of the present invention is not meant to be solely limited thereto. Other metals or bases such as, but not limited to, potassium and potassium hydroxide, respectively, or mixtures thereof are contemplated by the disclosure of the present invention. [0028] Alkoxy dithiocarbonate compounds are utilized in some embodiments of the present invention and having the following general formula:

R13-!- f O - COOH '

wherein R4 and R5 are as defined hereinabove; wherein R13 is optionally substituted, and can be a linear or branched alkyl having from 1 to about 12 carbon atoms; an aryl group, optionally saturated or unsaturated; an arylalkyl having from 7 to about 18 carbon atoms; an acyl group; an alkenealkyl having from 3 to about 18 carbon atoms; an alkene group; an alkylene group; an alkoxyalkyl; derived from a polyalkylene glycol; derived from a polyalkylene glycol monoalkyl ether having from 3 to 200 carbon atoms; derived from a polyalkylene glycol monoaryl ether having from 3 to 200 carbon atoms; a polyfluoroalkyl such as 2-trifluoroethyl; a phosphorous containing alkyl; or a substituted or unsubstituted aryl ring containing heteroatoms. Alkyl and alkylene groups from 1 to 6 carbon atoms are preferred; wherein the R13 substituents comprise an alkyl having from 1 to 6 carbon atoms; an aryl; a halogen such as fluorine or chlorine; a cyano group; an amino group; an alkene group; an alkoxycarbonyl group; an aryloxycarbonyl group; a carboxy group; an acyloxy group; a carbamoyl group; an alkylcarbonyl group; an alkylarylcarbonyl group; an arylcarbonyl group; an arylalkylcarbonyl group; a phthalimido group; a maleimido group; a succinimido group; amidino group; guanidimo group; allyl group; epoxy group; alkoxy group; an alkali metal salt; a cationic substitutent such as a quaternary ammonium salt; a hydroxyl group; an ether having a total of from 2 to about 20 carbon atoms such as methoxy, or hexanoxy; a nitro; sulfur; phosphorous; a carboalkoxy group; a heterocyclic group containing one or more sulfur, oxygen or nitrogen atoms, or combinations thereof; and wherein "a" is 1 to about 4, with 1 or 2 preferred. [0029] In the thiocarbonate compound embodiments set forth herein, the heteroatom(s) that are contained in the enumerated heteroatom containing substituents can be selected from nitrogen, oxygen, and sulfur and combinations thereof. Generally, a heteroatom containing substituent contains one or two heteroatoms. [0030] The compounds of the above formula are generally identified as O- alkyl-S~(α,α'-disubstituted-α"-acetic acid) xanthates. The O-alkyl-S-(α,α'- disubstituted-α"-acetic acid) xanthates are generated as the reaction product of an alkoxylate salt, carbon disulfide, a haloform, and a ketone. Alternatively, a metal salt of xanthate can be utilized in place of the alkoxylate salt and carbon disulfide. [0031] The general reaction mechanism for forming the O-alkyl-S-(α,α'- disubstituted-α"-acetic acid) xanthates is as follows:

R13O-Na+ + CS9

R4 acid Ria_ o - c- S- C- COOH

wherein R4, R5, and R13 are defined herein. [0032] As described hereinbelow and in the patents and applications incorporated herein by reference, the thiocarbonate compounds of the present invention can be reacted with one or more different monomers through a polymerization process, such as RAFT polymerization thereby incorporating the monomers into the backbone of the thiocarbonate compound thus forming thiocarbonate polymers or copolymers. The polymerization process is described hereinbelow with respect to the hydroxyl terminated thiocarbonate compound, but it is to be understood that thiocarbonate compounds having other terminal groups such as unsaturated groups can also be RAFT polymerized as described. Curable Thiocarbonate Urethanes A) Hydroxyl Terminated Thiocarbonate Compounds, Polymers and Copolymers [0033] The acid group terminated thiocarbonate compounds are reacted with a polyfunctional alcohol such as a diol or other polyol to form various hydroxyl terminated thiocarbonate compounds. Accordingly, monohydroxyl thiocarbonates, and dihydroxyl thiocarbonates or other polyol compounds are formed. [0034] Suitable polyols which are reacted with the thiocarbonate compounds

have the formula: wherein, the hydroxyl groups are not attached to the same carbon atom, and wherein n is 1 to 7 and preferably is 1. R14 can preferably be part of at least one simple or substantially hydrocarbon polyol, or less desirably part of at least one complex polyol. R14 is an alkyl or substituted alkyl or alkylene group having 2 to 200 carbon atoms and desirably from 2 to about 10 carbon atoms. The hydroxyl groups can be at the terminals of a main chain, or a branched chain, or a cyclic chain. The substituted alkyl or alkylene can contain oxygen, ether, ester, sulfide, halide, cyano and any heterocyclic rings including carbohydrates. [0035] The so-called simple or substantially hydrocarbon polyhydroxyl compounds are highly preferred and have alkyl or alkylene groups with the substituted alkyl or alkylene groups containing oxygen or a halide. Specific examples include ethylene glycol, 1 ,2- and 1 ,3-propylene glycols, 1 ,2-, 1 ,3-, 1 ,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1 ,6-hexanediol, 1 ,8-octanediol, and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethanol (1 ,4-bis-hydroxymethylcyclohexane), 2-methyl-1 ,3- propanediol, 2,2,4-trimethyl-1 ,3-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, dimerate diol, trimethylol propane, pentaerythritol, hydroxylated bisphenols, halogenated diols, and the like, and mixtures thereof. Highly preferred diols include ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, butylene glycol, hexane diol, and neopentyl glycol. [0036] Examples of complex polyols which are not desired but can be utilized include higher polymeric polyols such as polyester polyols and polyether polyols, as well as polyhydroxy polyester amides, hydroxyl-containing polycaprolactones, hydroxyl-containing (meth)acrylic interpolymers, hydroxyl-containing epoxides, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polythioethers, polysiloxane polyols, ethoxylated polysiloxane polyols, polybutadiene polyols and hydrogenated polybutadiene polyols, polyacrylate polyols, halogenated polyesters and polyethers, and the like, and mixtures thereof. The polyester polyols, polyether polyols, polycarbonate polyols, polysiloxane polyols, polyacetals, and ethoxylated polysiloxane polyols are preferred. [0037] The polyester polyols typically are esterification products prepared by the reaction of organic polycarboxylic acids or their anhydrides with a stoichiometric excess of a diol. Examples of suitable polyols for use in the reaction include poly(glycol adipate)s, poly(ethylene terephthalate) polyols, polycaprolactone polyols, orthophthalic polyols, sulfonated and phosphonated polyols, and the like, and mixtures thereof. [0038] The diols used in making the polyester polyols include alkylene glycols having from 2 to about 20 total carbon atoms, e.g., ethylene glycol, 1 ,2- and 1 ,3-propylene glycols, 1 ,2-, 1,3-, 1 ,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1 ,6-hexanediol, 1 ,8-octanediol, and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethano! (1 ,4-bis- hydroxymethylcyclohexane), 2-methyl-1 ,3-propanediol, 2,2,4-trimethyl-1 ,3- pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, dimerate diol, Trimethylol propane, pentaerythritol hydroxylated bisphenols, polyether glycols, halogenated diols, and the like, and mixtures thereof. Highly preferred diols include ethylene glycol, diethylene glycol, butylene glycol, hexane diol, and neopentyl glycol. [0039] Suitable carboxylic acids used in making the polyester polyols generally have from 1 to about 20 total carbon atoms and include dicarboxylic acids and tricarboxylic acids and anhydrides, e.g., maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric anhydride, adipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorendic acid, 1 ,2,4-butane-tricarboxylic acid, phthalic acid, the isomers of phthalic acid, phthalic anhydride, fumaric acid, dimeric fatty acids such as oleic acid, and the like, and mixtures thereof. Preferred polycarboxylic acids used in making the polyester polyols include aliphatic or aromatic dibasic acids. [0040] The preferred polyester polyol is a diol. Preferred polyester diols include poly(butanediol adipate); hexane diol adipic acid and isophthalic, acid polyesters such as hexane adipate isophthalate polyester; hexane diol neopentyl glycol adipic acid polyester diols, e.g., Piothane 67-3000 HNA (Panolam Industries) and Piothane 67-1000 HNA; as well as propylene glycol maleic anhydride adipic acid polyester diols, e.g., Piothane 50-1000 PMA; and hexane diol neopentyl glycol fumaric acid polyester diols, e.g., Piothane 67-500 HNF. Other preferred polyester diols include Rucoflex.RTM. S1015-35, S1040-35, and S-1040-110 (Bayer Corporation). [0041] Polyether diols may be substituted in whole or in part for the polyester diols. Polyether polyols contain from 2 to about 15 carbon atoms in the repeat unit and are obtained in known manner by the reaction of (A) the starting compounds that contain reactive hydrogen atoms, such as water or the diols set forth for preparing the polyester polyols, and (B) alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like, and mixtures thereof. Preferred polyethers include poly(propylene glycol), polytetrahydrofuran, and copolymers of poly(ethylene glycol) and poly(propylene glycol). [0042] Polycarbonates include those obtained from the reaction of (A) diols such 1,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like, and mixtures thereof with (B) diarylcarbonates such as diphenylcarbonate or phosgene. [0043] Polyacetals include the compounds that can be prepared from the reaction of (A) aldehydes, such as formaldehyde and the like, and (B) glycols such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-dihydroxy- diphenyldimethylmethane, 1 ,6-hexanediol, and the like. Polyacetals can also be prepared by the polymerization of cyclic acetals. [0044] Polysiloxanes include polydialkylsiloxane diols wherein the alkyl group has from 1 to about 3 carbon atoms such as polydimethylsiloxane diol made by GE such as OSI-14209, and by GEL-EST such as DMS-C21. [0045] The aforementioned diols useful in making polyester polyols can also be used as additional reactants to prepare the isocyanate terminated prepolymer. [0046] The hydroxyl terminated thiocarbonate compounds are formed by combining the desired thiocarbonate and base diol or polyol in a suitable reaction vessel. The reaction is an esterification and the same is known to the art and to the literature. For example, usually an acid catalyst such as p-toluenesulfonic acid is utilized and a reaction temperature is from about 200C to about 2000C and preferably from about 800C to about 1500C. The number of repeat units derived from the thiocarbonate compounds in the hydroxyl terminated thiocarbonate compositions ranges generally from about 1 to about 20, and desirably from about 1 to about 10. [0047] For example, a general reaction mechanism for preparing a trithiocarbonate diol is:

HOOC - C - S - C - S - C - COOH + HO - R14 - OH Catalyst >

Formula A

H - O { R14 - O - R14 - OH + H2O

Formula AA

wherein "a" is from about 1 to about 10 or about 20, and desirably from about 1 to about 5, and R1, R2 and R14 are defined herein above. The number of repeat groups "a" will vary depending upon the equivalent ratio of hydroxyl groups to carboxylic acid groups. Thus, when the OH/COOH ratio is preferably about 2 or greater, generally about one "a" unit will predominate, and the product can be a mixture of different "a" numbers. [0048] A general reaction mechanism for preparing a trithiocarbonate polyol utilizing the trithiocarbonate of Formula B is as follows.

R1 R3_ S-C-S-C-COOH +HO -R14 -OH Catalyst R2 Formula B

S R1 O " I Il ^ R3 -S-C-S-C-C- OR14 - O-H R2

Formula BB where R1, R2, R3, and R14 are defined as hereinabove. In order to form a hydroxyl terminated compound as set forth in Formula BB, the equivalent ratio of hydroxyl groups to carboxylic acid end groups, i.e. OH/COOH is preferably about 2 or greater. If lower equivalent ratios are utilized, non-hydroxyl terminated compounds can exist. [0049] The general reaction for preparing a dithiocarbamate polyol of Formula C where j is 1 is as follows:

COOH + HO-R14-OH Cata'ySt>

Formula C

Formula CC (j - 1) where R4, R5, R14, and R6 and R7 are defined herein above. In order to form a hydroxyl terminated compound as set forth in Formula CC, the equivalent ratio of hydroxyl groups to carboxylic acid end groups, i.e. OH/COOH is preferably about 2 or greater. If lower equivalent ratios are utilized, non-hydroxyl terminated compounds can exist. [0050] Reaction of the above dithiocarbamate C compound wherein j is 2 is as follows:

OOH + HO - R14 - OH Catalyst >

Formula C

H - O 4 / R14 - O + H2O

Formula CC ( j = 2)

where R4, R5, R14, and T are as defined herein above and "c" is from about 1 to about 10 or about 20 and desirably from about 1 to about 5. The number of repeat groups "c" will vary depending upon the equivalent ratio of hydroxyl groups to carboxylic acid groups. Thus, when the OH/COOH ratio is preferably about 2 or greater, generally about one "c" unit will predominate, and the product can be a mixture of different "c" numbers. [0051] When the dithiocarbonate is an alkoxy dithiocarbonate of Formula E, j can be 1 or 2. Where j = 1 , the general reaction is as follows: HO - R14 - OH Cata|yst >

Formula E

Formula EE (j = 1)

wherein R4, R5, and R13 are defined hereinabove. In order to form a hydroxyl terminated compound as set forth in Formula EE, the equivalent ratio of hydroxyl groups to carboxylic acid end groups, i.e., OH/COOH is preferably about 2 or greater. If lower equivalent ratios are utilized, non-hydroxyl terminated compounds can exist. [0052] When the dithiocarbonate is an alkoxy dithiocarbonate of Formula E wherein j = 2, the general reaction is as follows:

R4 β S R4 HOOC - C - S - C - O - R13 - O - C - S - C - COOH + HO - R14 - OH CatalySt » R5 R5

Formula E (where j = 2)

H H2O

Formula EE ( where j = 2)

where R4, R5, and R13, are defined herein above and "e" is from about 1 to about 10 or about 20, and desirably from 1 to about 5. The number of repeat groups "e" will vary depending upon the equivalent ratio of hydroxyl groups to carboxylic acid groups. Thus, when the OH-COOH ratio is preferably about 2 or greater, generally about one "e" unit will predominate, and the product can be a mixture of different "e" numbers. [00S3] In a similar manner, the reaction of other thiocarbonate compounds and other polyols will form hydroxyl terminated thiocarbonate polymers.

Monomer Incorporation [0054] In a further embodiment, the thiocarbonate compounds and/or the hydroxyl terminated thiocarbonate compounds are reacted with one or more, same or different monomers through a polymerization process, such as a reversible addition - fragmentation transfer (RAFT) polymerization, thereby incorporating the monomer(s) into the backbone of the thiocarbonate compound thus forming a thiocarbonate polymer or copolymer. Although the one or more monomers can first be reacted into the thiocarbonate compounds, it is preferred that the thiocarbonate compounds are reacted to contain hydroxyl end groups before the one or more monomers are reacted into the backbone of the thiocarbonate. [0055] The monomers include one or more conjugated diene monomers or one or more vinyl containing monomers, or combinations thereof. The various one or more free radically polymerizable monomer as well as the various reaction conditions thereof including types of initiators, catalysts, solvents, and the like are set forth in U.S. Patent Nos. U.S. Patent 6,596,889 granted July 22, 2003; U.S. Application Serial No. 10/219,403 filed 08/15/02; U.S. Application Serial No. 10/278,335 filed 10/23/02; and U.S. Application Serial No. 10/681 ,679 filed 10/08/03, all of which are hereby fully incorporated by reference with regard to all aspects thereof. [0056] The diene monomers have a total of from 4 to about 12 carbon atoms and examples include, but are not limited to, 1,3-butadine, isoprene, 1 ,3-pentadiene, 2,3-dimethyl-1-3~butadeine, 2-methyl-1 ,3-pentadiene, 2,3-dimethyi-1 ,3-pentadiene, 2-phenyl-1 ,3-butadiene, and 4,5-diethyl-1 ,3- octadiene, and combinations thereof. [0057] The vinyl containing monomers have the following structure:

where R15 comprises hydrogen, halogen, Ci to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc or the like or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl; and R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen. R17, independently, comprises C1-C18 alkyl, substituted Ci-C18 alkyl, C2-C18 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, dicyanato, cyano, silyl, halo and dialkylamino. Optionally, the monomers comprise maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo- polymerizable monomers. Monomers CH2 = CR15R16 as used herein include C1-C8 acrylates and methacrylates, acrylate and methacrylate esters, acrylic and methacrylic acid, styrene, α methyl styrene, C11-C12 alkyl styrenes with substitute groups both either on the chain or on the ring, acrylamide, methacrylamide, N- and N,N-alkylacrylamide 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 steric and electronic properties. The factors which determine copolymerizability of various monomers are well documented in the art. For example, see: Greenley, R.Z., in Polymer Handbook, 3rd Edition (Brandup, J., and Immergut, E. H. Eds.) Wiley: New York, 1989 pll-53. [0058] Specific monomers or comonomers include the following: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate (all isomers), butyl (meth)acrylate (all isomers), 2-ethylhexyl (meth)acrylate, isobomyl (meth)acrylate, (meth)acrylic acid, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylonitrile, alpha-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate (all isomers), (meth)acrylic acid, acrylonitrile, styrene, functional (meth)acrylates, (meth)acrylates such as glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate (all isomers), hydroxybutyl (meth)acrylate (all isomers), N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and triethyleneglycol (meth)acrylate, itaconic anhydride, itaconic acid; metal salts such as but not limited to sodium and zinc of all monomeric acids, such as but not limited to, itaconic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid, or the like; N-vinylimidazole, vinylpyridine N-oxide, 4-vinylpyridine carboxymethylbetaine, diallyl dimethylammonium chloride, p-styrenesulfonic acid, p-styrenecarboxylic acid, 2-dimethylaminioethyl acrylate and its alkyl/hydrogen halide salts, 2-dimethyl- aminoethyl methacrylate and its alkyl/hydrogen halide salts, N-(3-dimethyl- aminopropyl) acrylamide, N-(3-dimethylaminoproyl) methacrylamide, diacetone acrylamide, 2-(acetoacetoxy)ethyl methacrylate, 2-(acryloyloxy)ethyl acetoacetate, 3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy, etc), glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethyl acrylate, triethyleneglycol acrylate, methacrylamide, N-methylacrylamide, N,N-dimethyl- acrylamide, N-tertbutylmethacrylamide, N-N-butylmethacrylamide, N-methylol- methacrylamide, N-ethylolmethacrylamide, N-tertbutylacrylamide, N-N-butyl- acrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (all isomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoic acid (all isomers), diethylamino alpha-methylstyrene (all isomers), p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxy- methylsilylpropyl methacrylate, diethoxymethylsilylpropyl methacrylate, dibutoxy- methylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxy silylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxy- methylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxy-methylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxy-silylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl amiate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole, butadiene, isoprene, chloroprene, ethylene, and propylene, and combinations thereof. [0059] Preferred monomers are Ci-Ci8 (meth)acrylates; (meth)acrylic acid; Ci-C8 monoalkyl and dialkyl acrylamides; a combination of Ci-C8 (meth)acrylates; a combination of said acrylamides and Ci-C8 monoalkyl and dialkyl methacrylamides; styrene; butadiene; isoprene and acrylonitrile. [0060] 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 thiocarbonate 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 thiocarbonates compounds of the present invention. [0061] 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'-azobis(isobutyronitrile)(AIBN), 2,2'-azobis(2-cyano-2-butane), dimethyl 2,2'- azobisdimethylisobutyrate, 4,4'-azobis(4-cyanopentanoic acid), 1 , 1 '-azobis(cyclohexanecarbanitrile), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1 , 1 )-bis(hydoxymethyl)-2-hydroxyethyl] propionamide, 2,2'-azobis[2-methyl-N-hydroxyethyl)]-propionamide, 2,2'-azobis(N,N'- dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis(2- amidinopropane) dihydrochloride, 2,2'-azobis(N,N'- dimethyleneisobutyramine), 2,2'-azobis(2- methyl-N-[1 ,1- bis(hydroxymethyl)-2-hydroxyethyl] propionamide), 2,2'~azobis(2-methyl- N-[1 ,1-bis(hydroxymethyl) ethyl] propionamide), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) propionamide], 2,2'-azobis(isobutyramide) dehydrate, 2,2'-azobis(2,2,4-trimethylpentane), 2,2'-azobis(2-methylpropane), t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate, t-butylperoxy- neodecanoate, t-butylperoxy isobutyrate, t-amyl peroxypivalate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide, dilauroylperoxide, potassium peroxy- disulfate, ammonium peroxydisulfate, di-t-butyl hyponitrite, dicumyl hyponitrite.

[0062] 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, benzophenone, acyl phosphine oxides, and photo-redox systems production under the conditions of the polymerization; these initiating systems can include combinations of the following oxidants and reductants: oxidants: potassium peroxydisulfate, hydrogen peroxide, t-butyl hydroperoxide reductants: iron (11), titanium (111), potassium thiosulfite, potassium bisulfite. [0063] Other suitable initiating systems are described in recent texts. See, for example, Moad and Solomon "The Chemistry of Free Radical Polymerization". Pergamon, London. 1995. pp 53-95. [0064] In one embodiment the initiators of the present invention are 2,2'-azobis(isobutyronitrile)(AIBN), or 4,4'-azobis(4-cyanopentanoic acid), or 2,2'-azobis(2-cyano-2-butane), or 1 ,1'-azobis(cyclohexanecarbanitrile). 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, 10, 15, 20, or 25 mole percent based on the total moles of chain transfer agent utilized, i.e., said s,s'-bis-(α,α'- disubstituted-α"-acetic acid) - trithiocarbonates compounds. In order to form polymers which are predominately telechelic, initiators other than the above thiocarbonate 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. [0065] Optionally, as noted above, solvents can be utilized in the free radical polymerization process. Examples of such solvents include, but are not limited to, C6-C12 alkanes, ethyl acetate, toluene, chlorobenzene, acetone, t-butyl alcohol, n-methylpyrrolidone, 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 10 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. [0066] The one or more conjugated diene and/or vinyl monomers can be incorporated into the backbone of the thiocarbonate compound before it is reacted with a polyol and the same reaction scheme is set forth in U.S. Patent 6,596,899 granted July 22, 2003, or in U.S. Patent Application 10/278,335 filed 10/23/02, or in U.S. Patent Application 10/681 ,679 filed 10/08/03 which are hereby fully incorporated by reference. [0067] Alternatively, and in a similar manner, the various one or more conjugated diene monomers and/or the one or more vinyl monomers are incorporated into the backbone of the hydroxyl-terminated thiocarbonate compound. [0068] With respect to the hydroxyl terminated thiocarbonate of Formula AA, the general reaction scheme for reacting one or more conjugated diene monomers and/or one or more vinyl monomers into the backbone of the hydroxyl- terminated trithiocarbonate compound is as follows:

Monomer Catalyst

Formula AA

Block Formula AA or

Block Formula AA' wherein R1, R2, R14, R15, and R16 are defined hereinabove, "a" is as set forth

hereinabove, and m, m', n and n', independently, is generally from about 1 to

about 10,000, desirably from about 2 to about 500, and preferably from about 5 to

about 100. Naturally, any remaining monomer is removed.

[0069] With respect to the hydroxyl-terminated trithiocarbonate compound of

Formula BB, the general reaction scheme is as follows:

S R1 O Il I Il R3 - S - C - S - C - C - OR14 - O-H+ Monomer + Catalyst

R2 ^ Formula BB

' repeat group(s) derived from vinyl R containing R3 - S - C - S - monomers, or con¬ - 9 C - OR1144 - O-H jugated diene monomers, or . combinations thereof m

Block Formula BB

or

Block Formula BB'

wherein R1, R2, R3, R14, R15, and R16 are defined hereinabove, and m and m\

independently, is generally from about 1 to about 10,000, desirably from about 2

to about 500, and preferably from about 5 to about 100. Naturally, any remaining

monomer is removed.

[0070] With regard to the hydroxyl-terminated trithiocarbonate compound of

Formula CC where j is 1 , the general reaction scheme is as follows: R6X S R4 O N-C-S-C-C-O- R14 -O-H + Monomer + Catalyst

R / R5 Formula CC (j=1)

repeat group(s) R derived from vinyl R4 O \ containing r N-C-S monomers, or con¬ -C-C-O- R14 -O- H jugated diene / monomers, or R7 _ combinations thereof m Block Formula CC (j=1)

or

Block Formula CC

wherein R4, R5, R6, R7, R14, R15, and R16 are defined hereinabove, and m and m'

is generally from about 1 to about 10,000, desirably from about 2 to about 500,

and preferably from about 5 to about 100. Naturally, any remaining monomer is

removed.

[0071] With respect to the high temperature dithiocarbonate compound of

Formula CC where j is 2, the general reaction scheme is as follows.

O

H-O-|R14-O-C-

Formula CC ( j = 2)

Block Formula CC

or

H-f O-R14-O -O4R14-OH

Block Formula CC

wherein R4, R5, R14, R15, R16, and T are defined hereinabove, wherein c is from

about 1 to about 10 or about 20, and preferably from 1 to about 5, and wherein m,

m', n, and n\ independently, are generally from about 1 to about 10,000, desirably

from about 2 to about 500, and preferably from about 5 to about 100. Naturally,

any remaining monomer is removed.

[0072] With respect to the high temperature dithiocarbonate of Formula EE, the

general reaction scheme is as follows:

st

Formula EE

repeat group(s) derived from vinyl containing R4 O monomers, or con¬ R13 — O -C— S - j"ugated diene C C -O-R14 - O - H monomers, or combinations thereof R5 m Block Formula EE

or R4 O Ri3_o-c— s 4 C-CH -C C-O-R14-O-H R16 R5 m1

Block Formula EE'

wherein R4, R5, R13, R14, R15, and R16, are defined hereinabove, wherein m and m'

is generally from about 1 to about 10,000, desirably from about 2 to about 500,

and preferably from about 5 to about 100. Naturally any remaining monomer is

removed.

[0073] With respect to the hydroxyl-terminated dithiocarbonate of Formula EE

where j is 2, the general reaction scheme is as follows:

O R4 s s R4

H OiR14 - O- C - C - S - C - O - R13 - O - C - S - C - C - O R14 - OH + Monomer + Catalyst R5 R5 Formula EE where j is 2

repeat group(s) o R4 derived from vinyl repeat group(s) S S derived from vinyl containing < " containing H 0[R14 - O- C - C - monomers, or 11 S-C-O- R13 -O -C -S monomers, or R14 - OH conjugated diene conjugated diene R5 monomers, or monomers, or combinations thereof combinations thereof m

Block Formula EE where j is 2

or

Block Formula EE' where j is 2 wherein R4, R5, R13, R14, R15, and R16, are defined hereinabove, wherein e is from about 1 to about 10 or about 20, and preferably from about 1 to about 5, and wherein m, m', n, and n\ independently, is from about 1 to about 10,000, desirably from about 2 to about 500, and preferably from about 5 to about 100. Naturally any remaining monomer is removed. [0074] Reactions of other thiocarbonates with various conjugated diene and/or vinyl monomers react in a similar manner, and reaction mechanisms are set forth in more detail in U.S. Patent No. 6,596,899 issued July 22, 2003; U.S. Patent Application Serial Nos. 10/219,403 filed 8/15/02; 10/278,335 filed 10/23/02; and 10/681 ,679 filed 10/08/03 which are hereby fully incorporated by reference. [0075] The resulting polymers or copolymers are either telechelic polymers with hydroxyl functional groups at both ends of the chain, or a polymer having a single hydroxyl functional end group and also a small amount of 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 depend on the amount of initiator utilized. The greater the amount of the other initiator utilized proportionally decreases the amount of telechelic polymers formed. Generally, the number of the repeat groups of the one or more monomers per polymer chain such as m, m', n or n' have a wide range as set forth above. 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 hydroxyl terminated thiocarbonate polymers or copolymers of the present invention can be the same or different. That is, random copolymers, terpolymers, etc., can be formed within the one or more m, m\ n, or n' blocks as noted, as well as block copolymers can be formed by initially adding one monomer and then subsequently adding a different monomer (e.g. an internal block copolymer). [0076] 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 400C to about 800C, when 4,4'-azobis(4-cyanovaleric) acid is utilized, the temperature generally is from about 50°C to about 9O0C, when di-t-butylperoxide is utilized, the temperature generally is from about 11O0C to about 16O0C, when a thiocarbonate is utilized, the temperature is generally from about 8O0C to about 2000C.

Example 1 [0077] Synthesis of the monohydroxyl terminated dithiocarbamate compound

Procedure: [0078] In a 1000 ml jacketed reaction vessel equipped with a mechanical stirrer, a thermometer, a reflux condenser, distillation adaptor, and an addition funnel, 500 grams of ethylene glycol was added and heated to 90°C under nitrogen. A mixture of 200 grams of the dithiocarbonate and 18.37 grams of the p-toluenesulfonic acid monohydrate was added through the addition funnel dropwise to maintain reaction temperature. A mixture of dithiocarbonate and p-toluenesulfonic acid was added, heated to 11O0C and 60 mm Hg of partial vacuum was pulled to collect water. When no more water was collected and the head temperature dropped and levels dropped off, the vacuum was slowly increased to full vacuum to distill off excess ethylene glycol. When reaction temperature exceeded 900C, the reaction was stopped. For purification, 250 ml toluene was added when the reaction had cooled and stirred to room temperature. The mixture was then transferred to a separatory funnel and extracted three times with 100 ml saturated sodium carbonate. The aqueous fractions were discarded and the organic (toluene) fraction collected. 10 grams of magnesium sulfate was added. After one hour, the filter contents were concentrated with a rotavaporator at 800C, full vacuum, for an hour. An orange, viscous product was collected and the structure confirmed with mass spectrometry, nuclear magnetic resonance and hydroxyl number.

Example 2 [0079] Synthesis of dihydroxyl dithiocarbamate compound

Procedure: [0080] In a 500 ml jacketed reaction vessel equipped with a mechanical stirrer, a thermometer, a reflex condenser, distillation adaptor, and an addition funnel, 150 grams of ethylene glycol and 5.57 grams of the p-toluenesulfonic acid monohydrate was added and heated to 110°C under nitrogen. A mixture of 60 grams of the dithiocarbonate was added through the addition funnel dropwise to maintain reaction temperature. Once added, the partial vacuum was increased to 60 mm Hg to remove water. When little water was coming off and head temperature dropped and levels dropped off, the temperature was increased to 1200C to remove more water. When no more water was removed and head temperature dropped and stabilized, the vacuum was increased to full vacuum to remove excess ethylene glycol. When temperature exceeded 110°C, the heat was turned off. When reaction was room temperature, added 65 ml methyl isobutyl ketone and stirred till homogenous. Added 33 ml of 5% sodium hydroxide, stirred and transferred to a separatory funnel. Collected organic (methyl isobutyl ketone) fraction. Extracted aqueous layer two times each with 16ml methyl isobutyl ketone. Added these two methyl isobutyl ketone fractions to the previous organic fraction. The organic fraction was stirred at room temperature until a white precipitate dropped out and became thick. Refrigerated, buchner filtered and collected white solid. Confirmed structure by nuclear magnetic resonance, mass spectrometry and hydroxyl number.

Example 3 [0081] Synthesis of Monohydroxyl Dithiocarbamate Polymer Containing Repeat Units Derived from Ethyl Acrylate

CH3 S \ CH3 OH Il N - C - S - (EA)n i whe e m = about 18 Cf O ^ r / CH3 CH3

Procedure: [0082] In a 1000 ml reaction vessel equipped with mechanical stirrer, thermometer, reflux condenser and nitrogen purge, 44.2 grams of the monohydroxyl terminated dithiocarbonate, 395.9 grams of ethyl acrylate, 400 ml of MEK, and 0.5071 grams of Azo catalyst were added. After a nitrogen blanket was applied, the reactants were heated to 650C. After no further exotherm was observed, the reactants were heated to 8O0C for a period of about 5 hours. The solvent was removed by rotavaporation under full vacuum and 8O0C and a viscous product collected. The structure was confirmed by size exclusion chromatography, hydroxyl number and matrix-assisted laser desorbtion ionization.

Example 4 [0083] Synthesis of Dihydroxyl Dithiocarbamate Polymer Containing Repeat Units Derived from Butyl Acrylate

MEK

where m = about 9

Procedure:

[0084] In a 2000 ml reaction vessel equipped with mechanical stirrer,

thermometer, reflux condenser and nitrogen purge, 58.0 grams of the dihydroxyl

terminated dithiocarbonate, 524.33 grams of butyl acrylate, 0.3323 grams of Azo

catalyst, and 580 ml of MEK were added. After a nitrogen blanket was applied,

the reactants were heated to 65°C for a period of about 4.5 hours. Solvent was

removed by rotavaporation under full vacuum and 800C. The viscous product was

collected. Confirmed structure by size exclusion chromatography, hydroxyl

number and matrix-assisted laser de desorbtion ionization.

Example 5

[0085] Synthesis of a Dihydroxyl Dithiocarbamate Copolymer Containing

Repeat Units Derived from Ethyl Acrylate and Acrylonitrile

— — 5 C O/7" where m = about 9 and n = about 1.3

Procedure: [0086] In a 2000 ml reaction vessel equipped with mechanical stirrer, thermometer, reflux condenser and nitrogen purge, 124.5 grams of the monohydroxyl terminated dithiocarbonate, 465 grams of ethyl acrylate, 35 grams of acrylonitrile, 0.9611 grams of Azo catalyst, and 625 ml of dimethylforamide were added. After a nitrogen blanket was applied, the reactants were heated to 65°C for a period of about 8.5 hours. Solvent was removed by rotavaporation under full vacuum and 800C. The viscous product was collected. Confirmed structure by size exclusion chromatography, hydroxyl number and matrix-assisted laser desorbtion ionization.

Thermoplastic including Linear Polyurethanes (TPU) made from hydroxyl- terminated thiocarbonate compounds, polymers, and copolymers. [0087] Thermoplastic polyurethanes are generally formed in one embodiment of the invention by reacting the hydroxyl group terminated thiocarbonate compounds, polymers, or copolymers, or a combination thereof with an isocyanate group-containing compound optionally in the presence of a catalyst generally followed by chain extension. The thermoplastic urethanes can be made by can be made preferably by a waterborne process, or by a solvent process, or by extrusion. Optionally thermosets can be formed utilizing either crosslinking agents or self-crosslinking compounds incorporated within various urethane components. The term "polyurethane composition" when utilized in the specification generally refers to a composition containing reagents utilized to form a polyurethane, or a composition subsequent to the reaction of the polyurethane forming reagents by some process or mechanism. The thermoplastic polyurethanes of the invention are able to be melted and reshaped by some process such as extrusion or molding, or cast into film from solution and are thus substantially uncrosslinked.

Isocyanates [0088] Suitable isocyanates comprise mono-isocyanates and polyisocyanates such as di-isocyanates, tri-isocyanates, and functionalized isocyanates having a total of from 4 to about 10, or about 15, or about 20 carbon atoms, or mixtures thereof. In one embodiment, suitable isocyanates have an average of one or more, or about two to about four isocyanate groups, preferably an average of about two isocyanate groups and include aliphatic, cycloaliphatic, aromatic including any aliphatic groups, and trialkoxysilylalkyl isocyanates, used alone or in mixtures of two or more. Diisocyanates are highly preferred in order to produce thermoplastic polyurethanes. [0089] Specific examples of suitable aliphatic polyisocyanates include alpha, omega-alkylene diisocyanates having from 5 to about 20 carbon atoms, such as tetramethylene diisocyanate, hexamethylene-1 ,6-diisocyanate (HDI), decamethylene diisocyanate, 1 ,12-dodecane diisocyanate, 2,2,4-trimethyl- hexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, 2-methyl-1 ,5-pentamethylene diisocyanate, and the like. Polyisocyanates having fewer than 5 carbon atoms can be used but are less preferred because of their high volatility and toxicity. Aromatic aliphatic isocyanates can also be used such as 1 ,2-, 1 ,3- and 1,4-xylylene diisocyanates and m-tetramethylxylyene diisocyanate (TMXDI). Preferred aliphatic polyisocyanates include hexamethylene-1 , 6-diisocyanate, 2,2,4-trimethyl-hexamethylene-diisocyanate, and 2,4,4-trimethyl-hexamethylene diisocyanate. [0090] Specific examples of suitable cycloaliphatic polyisocyanates contain from about 6 to about 20 carbon atoms and include cyclobutane-1 ,3-diisocyanate, 1 ,2-, 1 ,3- and 1 ,4-cyclohexane diisocyanates, 2,4- and 2,6-methylcyclohexane diisocyanate, 4,4'- and 2,4'-dicyclohexyldiisocyanates, 1 ,3,5-cyclohexane triisocyanates, isocyanatomethylcyclohexane isocyanates, isocyanatoethylcyclohexane isocyanates, bis(isocyanatomethyl)-cyclohexane diisocyanates, 4,4'- and 2,4'-bis(isocyanatomethyl) dicyclohexane, isophorone diisocyanate, and the like including derivatives, dimers, and trimers thereof. Preferred cycloaliphatic polyisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate. [0091] Examples of suitable aromatic polyisocyanates contain from about 8 to about 20 carbon atoms and include 2,4- and 2,6-hexahydrotoluenediisocyanate, 1 ,2, 1 ,3, and 1 ,4-phenylene diisocyanates, triphenyl methane-4,4', 4"-triisocyanate, naphthylene-1 ,5-diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), 2,4'-, 4,4'- and 2,2-biphenyl diisocyanates, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanates (MDI), polyphenyl polymethylene polyisocyanates (PMDI), mixtures of MDI and PMDI, mixtures of PMDI and TDI, and modified polyisocyanates derived from the above isocyanates and polyisocyanates, including dimers and trimers thereof, or combinations thereof. [0092] Examples of suitable trialkoxysilylalkyl isocyanates include trimethoxy- silylpropyl and triethoxysilylpropyl isocyanate. [0093] The mole equivalent ratio of all NCO groups to all OH terminated compounds such as hydroxyl terminated thiocarbonates, the various hydroxyl- terminated compounds such as polyols which are reacted with an isocyanate, the various dispersants, and the like is generally in excess so that chain extension subsequently can be carried out and generally is from about 1.0 or about 1.25 to about 5.0; desirably from about 1.4 to about 2.2 and more desirably from about 1.4 to about 2.0 with respect to waterborne prepolymers and generally lower with respect to solvent borne systems. lonic Dispersants, or Nonionic Dispersants. or combinations thereof [0094] Various ionic or nonionic dispersants known to the art and to the literature are generally utilized whenever a dispersion or a waterborne polyurethane is desired. The ionic dispersants can be compounds which contain the following cations:

-A± I + — P- or - S+ I I

or compounds which contain the following anions: — SO3 , — OSO3 , — PO2 , -PO3", -OPO3" or preferably —COO". [0095] When ionic dispersants are utilized, desirably they are subsequently neutralized, that is some and up to all of the ionic dispersants are neutralized with the requirement that a stable dispersion be produced. The amount of the dispersants neutralized will vary depending upon the type of the dispersant, the type of urethane polymer, and the like. [0096] With regard to the various anionic dispersants, e.g. acid dispersants, which are preferred, such compounds generally contain a hydrophilic functional group such as a carboxyl or hydroxyl so that the urethane can be dispersed into water, and may or may not be crosslinkable. A preferred class of anionic dispersants include hydroxy-carboxylic acids having the general formula (HO)χQ(COOH)y, wherein Q is a straight or branched hydrocarbon radical having 1 to 16 carbon atoms, and x and y are each, independently, 1 to 3, x preferably being 2 and y being 1. Examples of such hydroxy-carboxylic acids include citric acid, dimethylol propanoic acid (DMPA), dimethylol butanoic acid (DMBA), glycolic acid, thioglycolic acid, tartaric acid, dihydroxy tartaric acid, lactic acid, malic acid, dihydroxymalic acid. Dihydroxy-carboxylic acids are preferred with dimethylolpropanoic acid (DMPA) being most preferred. If desired, the carboxyl containing diol ortriol may be incorporated into a polyester by reaction with a dicarboxylic acid before being incorporated into the polyurethane prepolymer. [0097] When preparing polyurethane dispersions according to the invention the dispersing groups can be derived from ionic polyester polyols, and polycarbonate polyols. For example, in ionic polyester polyols, the ionic character which these polyols exhibit is based on the condensation of monomers which, in addition to the functional groups required for the condensation (for example hydroxyl, amino and carboxyl groups), contain sulfonic acid, carboxylic acid and/or phosphonic acid groups or sulfonate, carboxylate and/or phosphonate groups. A commercial example of an ionic/ionizable polyol are Lexorez 1405 - 65 (carboxylic acid functional polyester polyols obtained from Inolex Chemical Company). [0098] Nonionic dispersants include alkylene oxide compounds having repeat groups either in the backbone, or in the side chain (preferred), or combinations thereof. By the term "alkylene oxide" it is meant alkylene oxide and substituted alkylene oxide compounds having from 2 to 10 carbon atoms. Main chain nonionic dispersants generally have at least two repeat groups and desirably at least several repeat groups between the usually hydroxyl-terminated end groups of the oligomer or polymer. A preferred anionic dispersant is polyethylene glycol. [0099] The nonionic dispersants containing poly(alkylene oxide) side chains if used in this invention in an amount to subsequently partially or fully form a waterborne polyurethane; that is from about 0.1 to about 40 parts by weight and preferably about 5 to about 30 parts by weight, based upon the 100 parts by weight of the formed final polyurethane on a dry weight basis. At least about 50 wt. %, preferably at least about 70 wt. %, and more preferably at least about 90 wt. % of the poly(alkylene oxide) side-chain units comprise poly(ethylene oxide), and the remainder of the side-chain poly(alkylene oxide) units can comprise alkylene oxide and substituted alkylene oxide units having from 3 to about 10 carbon atoms, such as propylene oxide, tetramethylene oxide, butylene oxides, epichlorohydrin, epibromohydrin, allyl glycidyl ether, styrene oxide, and the like, and mixtures thereof. The term "final polyurethane" means the polyurethane produced after formation of the prepolymer followed by the chain extension step as described more fully hereafter. [0100] Compounds of poly(alkylene oxide) side-chains are known to those skilled in the art. For example, active hydrogen-containing compounds include various diols having repeat units of poly(alkylene oxide) side-chains (e.g. from about 5 to about 50 and desirably from about 15 or about 20 to about 30 or about 40) such as those described in U.S. Pat. No. 3,905,929 (hereby incorporated herein by reference in its entirety). Further, U.S. Pat. No. 5,700,867 (hereby incorporated herein by reference in its entirety) teaches methods for incorporation of poly(ethylene oxide) side-chains at col. 4, line 35 to col. 5, line 45. A preferred active hydrogen-containing compound having poly(ethylene oxide) side-chains is trimethylol propane monoethoxylate methyl ether, available as Tegomer D-3403 from Degussa-Goldschmidt. Tegomer D-3403 generally has an average side chain degree of polymerization of from about 15 to about 35 and desirably from about 22 to about 28 predominately ethylene oxide repeat units. The number average molecular weight of the preferred side-chain containing alkylene oxide monomers is generally from about 350 to about 5,000, and preferably from about 750 to about 2,000. [0101] Another class of nonionic dispersants include diisocyanates having pendent polyoxyethylene chains which may be used in the preparation of the nonionic prepolymer include those described in the prior art, for example in U.S. Patent 3,920,598, hereby fully incorporated by reference. These diisocyanates, because of their function, may be regarded as dispersing diisocyanates. Particularly suitable dispersing diisocyanates may be obtained by reacting two moles of an organic diisocyanate in which the two isocyanate groups have different reactivities with approximately one mole of a polyethylene glycol mono- ether, the initially formed urethane monoisocyanate then reacting at a higher temperature with the excess diisocyanate to form an allophanate diisocyanate having a pendent polyoxyethylene chain. [0102] While either an anionic or a nonionic dispersant can be utilized, it is within the ambit of the present invention to utilize blends or mixtures of both ionic or nonionic dispersants, as well as a dispersant which contain an ionic and a nonionic group or segment to achieve desired stable polyurethane dispersions. Catalysts [0103] Generally, any conventional thermoplastic polyurethane catalyst known to the literature and to the art can be utilized in preparing the thermoplastic polyurethane of the present invention. Such catalysts include organic and inorganic acid salts of, and organometallic derivatives of, bismuth, tin, iron, antimony, cobalt, thorium, aluminum, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese and zirconium, as well as phosphines, tertiary organic amines, and multi-functional polyalcohol amine catalysts. Representative organotin catalysts have from about 6 to about 20 carbon atoms and include stannous octoate, dibutyltin dioctoate, dibutyltin diluarate, and the like. Representative tertiary organic amine catalysts include triethylamine, triethylenediamine, N,N,N'N'-tetramethylethylenediamine, N1N1N1N'- tetraethylethylenediamine, N-methyl- morpholine, N-ethylmorpholine, N, N, N', N'- tetramethylguanidine, N,N,N',N'-tetramethyl-1 ,3-butanediamine, N,N-dimethylethanolamine, N,N-diethylethanol- amine, diazabicyclo[2.2.2]octane, and the like. Representative polyalcohol amine catalysts include triethanolamine, diethanolamine, or bis(2-hydroxyethyl)amino-2-propanol, and the like. [0104] The amount of catalyst employed is generally less than about 1000 and desirably less than about 400 parts by weight per million parts by weight of the total weight of the polyurethane forming reactants, i.e., polyisocyanate(s), the hydroxyl-terminated thiocarbonates whether or not they contain vinyl repeat units therein, and the chain extenders. Mixtures of the above noted catalysts can likewise be utilized. It is desirable to use minimal amounts of the catalyst in order to minimize side reactions. Preferred catalysts include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, and bismuth octoate.

Active Hydrogen Compounds or lsocyanate Reactive Compounds [0105] Although optional, it is an important aspect of the invention that active hydrogen or isocyanate reactive compounds, such as polyols, can be utilized in addition to the above-noted hydroxyl-terminated thiocarbonates whether or not they contain vinyl or other repeat units therein. The use of such active hydrogen or isocyanate reactive compounds is often desirable with regard to achieving suitable polyurethane end properties and occasionally can serve as a dispersant or a quasi dispersant. The term "polyol" denotes any high molecular weight compound, other than the hydroxy! terminated thiocarbonate compounds, polymers, and copolymers, such as polymers having an average of about two or more hydroxyl groups per molecule. Examples of such polyols that can be used in the present invention include so-called simple or substantially polyhydroxyl hydrocarbon polyols (preferred), as well as other polymeric polyols such as polyester polyols and polyether polyols, as well as polyhydroxy polyester amides, hydroxyl-containing polycaprolactones, hydroxyl-containing acrylic interpolymers, hydroxyl-containing epoxides, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polythioethers, polysiloxane polyols, ethoxylated polysiloxane polyols, polybutadiene polyols and hydrogenated polybutadiene polyols, polyacrylate polyols, halogenated polyesters or halogenated polyethers, and the like, and mixtures thereof. The polyester polyols, polyether polyols, polycarbonate polyols, and polysiloxane polyols are preferred. [0106] The so-called hydrocarbon polyols are generally diols having from 2 to about 12 or about 20 carbon atoms and preferably 2 to about 4 or about 6 or about 10 carbon atoms and include ethylene glycol, 1,2- and 1,3-propylene glycols, 1 ,2-, 1 ,3-, 1,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1 ,6-hexanediol, 1 ,8-octanediol, and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethanol (1 ,4-bis-hydroxymethylcyclohexane), 2-methyl-1 ,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, halogenated diols, and the like, and mixtures thereof. Preferred diols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexane diol, and neopentyl glycol. [0107] The polyester polyols typically are esterification products prepared by the reaction of organic polycarboxylic acids or their anhydrides with a stoichiometric excess of a diol. The diols used in making the polyester polyols include alkylene glycols having from 2 to about 20 total carbon atoms, e.g., ethylene glycol, 1 ,2- and 1,3-propylene glycols, 1,2-, 1,3-, 1,4-, and 2,3-butylene glycols, hexane diols, neopentyl glycol, 1 ,6-hexanediol, 1 ,8-octanediol, and other glycols such as bisphenol-A, cyclohexane diol, cyclohexane dimethano! (1 ,4-bis- hydroxymethylcyclohexane), 2-methyl-1 ,3-propanediol, 2,2,4-trimethyl-1 ,3- pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, dimerate diol, hydroxylated bisphenols, polyether glycols, halogenated diols, and the like, and mixtures thereof. Preferred diols include ethylene glycol, diethylene glycol, butylene glycol, hexane diol, and neopentyl glycol. Suitable carboxylic acids used in making the polyester polyols generally have from 1 to about 20 total carbon atoms and include dicarboxylic acids (preferred) and tricarboxylic acids and anhydrides, e.g., maleic acid, maleic anhydride, succinic acid, glutaric acid, glutaric anhydride, adipic acid (preferred), suberic acid, pimelic acid, azelaic acid, sebacic acid, chlorendic acid, 1 ,2,4-butane-tricarboxylic acid, phthalic acid, the isomers of phthalic acid, phthalic anhydride, fumaric acid, dimeric fatty acids such as oleic acid, and the like, and mixtures thereof. [0108] The preferred polyester polyol has two hydroxyl end groups. Preferred polyester diols include polyφutanediol adipate); hexane diol adipic acid and isophthalic acid polyesters such as hexane adipate isophthalate polyester; hexane diol neopentyl glycol adipic acid polyester diols, and neopentyl glycol adipic acid. [0109] Polythioether polyols which can be used include products obtained by condensing thiodiglycol either alone or with other glycols, dicarboxylic acids, formaldehyde, aninoalcohols or aminocarboxylic acids. [0110] Polyether diols may be substituted in whole or in part for the polyester diols. Polyether polyols contain from 2 to about 15 carbon atoms in the repeat unit and are obtained in known manner by the reaction of (A) the starting compounds that contain reactive hydrogen atoms, such as water or the diols set forth for preparing the polyester polyols, and (B) alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and the like, and mixtures thereof. Preferred polyethers include poly(propylene glycol), polytetrahydrofuran, and copolymers of poly(ethylene glycol) and poly(propylene glycol). [0111] Polycarbonates include those obtained from the reaction of (A) diols such 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like, and mixtures thereof with (B) diarylcarbonates such as diphenylcarbonate or phosgene. [0112] Polyacetals include the compounds that can be prepared from the reaction of (A) aldehydes, such as formaldehyde and the like, and (B) glycols such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-dihydroxy- diphenyldimethylmethane, 1 ,6-hexanediol, and the like. Polyacetals can also be prepared by the polymerization of cyclic acetals. [0113] The aforementioned diols useful in making polyester polyols can also be used as additional reactants to prepare the isocyanate terminated prepolymer. [0114] Of the above various one or more polyols which can be utilized, generally the hydrocarbon polyols, polyether polyols, polyester polyols; and polyhydroxy polycarbonates are preferred. The above-noted optional polyols can be utilized in association with a hydroxyl-terminated thiocarbonates in an amount of from about 0 or about 0.1 to about 80, desirably from about 1 to about 50 and preferably from about 2 to about 20 parts by weight per 100 total parts by weight of the final formed polyurethane.

Urethane Reaction Temperatures [0115] The polyurethane forming reaction is performed at temperatures generally from about 300C to about 2200C, desirably from about 4O0C to about 12O0C, and preferably from about 500C to about 1000C. Temperatures above about 2200C are generally avoided in order to prevent the polyurethanes from decomposing. Suitable mixing times in order to enable the various components to react and form the thermoplastic polyurethanes of the present invention are generally from about 1 to about 5 and desirably from about 2 to about 3 minutes. Prepolymer and Polymer Preparation Routes [0116] The preparation of a urethane prepolymer and/or polymer can generally be carried out according to one of three routes, that is a waterborne route, a solvent route, or a bulk route.

Waterborne Route - Neutralization [0117] Considering the waterborne route, one or more of the above noted ionic dispersants are utilized and the same must be neutralized generally before or during addition of the urethane prepolymer to water. Neutralization via the waterborne route involves, for example, converting the pendant carboxyl groups of an ionic (e.g. acid dispersant to a carboxylate anion, in the prepolymer, which has a water dispersability enhancing effect. Suitable neutralizing agents for the prepolymers are desirably tertiary amines having a total of from 1 to about 20 carbon atoms and desirably from about 1 to about 5 carbon atoms. Examples of suitable tertiary amines include triethyl amine (TEA), dimethyl ethanolamine (DMEA), N-methyl morpholine, and the like. Primary or secondary amines can also be used in lieu of tertiary amines if they are sufficiently hindered to avoid interfering with the chain extension process. Alternatively, alkaline hydroxides such as sodium hydroxide, potassium hydroxide, or ammonium hydroxide can be used. [0118] A preferred neutralization route is to first neutralize the urethane prepolymers containing an anionic dispersant therein and then subsequently add the same to water. A less preferred route is to add the neutralizing compound such as a tertiary amine to water and then to add the urethane prepolymer thereto. An amount of water is generally utilized such that an aqueous dispersion of the urethane prepolymer exists. Thus, an amount of water can be utilized to obtain a desired solids content after chain extension and/or crosslinking via the waterborne route such as from about 10 to about 70 and desirably from about 30 to about 55% by weight after chain extension. Waterborne Route - Chain Extension [0119] The active hydrogen-containing chain extender which is reacted with the waterbome prepolymer is desirably an amine because of its high rate of reactivity versus a diol or water, (which is a competing reaction). Suitable long- chain amines include polyester amides and polyamides, such as the predominantly linear condensates obtained from reaction of (A) polybasic saturated and unsaturated carboxylic acids or their anhydrides, and (B) polyvalent saturated or unsaturated aminoalcohols, diamines, polyamines, and the like, and mixtures thereof. Desired amine compounds include an amino alcohol, ammonia, a primary or secondary aliphatic, alicyclic, aromatic, araliphatic or heterocyclic amine having a total of from about 2 to about 20 carbon atoms, especially a diamine, urea or derivatives thereof, hydrazine or a substituted hydrazine. Water- soluble chain extenders are preferred. [0120] Examples of suitable chain extenders useful herein include ethylene diamine (EDA), diethylene triamine (DETA), triethylene tetramine (TETA), propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, piperazine, 2-methyl piperazine, phenylene diamine, 2-methylpentamethylenediamine, tolylene diamine, xylylene diamine, tris(2-aminoethyl) amine, 3,3'-dinitrobenzidine, 4,4'-methylenebis (2-chloroaniline), 3,3'-dichloro-4,4'-bi-phenyl diamine, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, menthane diamine, m-xylene diamine and isophorone diamine. Also, materials such as hydrazine, azines such as acetone azine, substituted hydrazines such as, for example, dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine, carbodihydrazine, hydrazides of dicarboxylic acids and sulfonic acids such as adipic acid mono- or dihydrazide, oxalic acid dihydrazide, isophthalic acid dihydrazide, tartaric acid dihydrazide, 1,3-phenylene disulfonic acid dihydrazide, and omega-amino-caproic acid dihydrazide. Hydrazides made by reacting lactones with hydrazine such as gamma- hydroxylbutyric hydrazide, bis-semi-carbazide, and bis-hydrazide carbonic esters of glycols such as any of the glycols mentioned above, and the like. [0121] Where the chain extender is other than water, for example a diamine or hydrazine, it may be added to the aqueous dispersion of prepolymer or, alternatively, it may already be present in the aqueous medium when the prepolymer is dispersed therein or added simultaneously. [0122] The chain extension of the waterborne urethane prepolymers can be conducted at elevated, reduced or ambient temperatures. Convenient temperatures are from about 5°C to 95°C or more, preferably from about 100C to about 45°C. [0123] With respect to waterborne systems, the ratio of the total number of equivalents of Zerewitinoff active hydrogen groups of all chain extenders utilized as compared to the total number of equivalents of isocyanate groups ranges generally from about 0.1 to about 2.0, desirably from about 0.15 to about 1.5, and preferably from about 0.3 to about 1.1. Of course, when water is utilized as a chain extender, the above ratios are not applicable since as well known to the art and to the literature, water can function both as a chain extender and a dispersing medium and will be present in a large excess relative to the amount of free NCO groups.

Solvent Route [0124] While not preferred, the various thermoplastic polyurethanes can be prepared by polymerization of the various components, for example an isocyanate compound, the hydroxy! terminated thiocarbonate, various active hydrogen compounds such as polyether diol, etc., and the like, in a solvent. Desired solvents include volatile hydrocarbons such as the various alkanes having from 5 to about 17 carbon atoms, for example pentane, hexane, heptane, octane, and the like, or various aromatic or hydrocarbons containing both an aromatic ring and an aliphatic group such as benzene, toluene, xylene, and the like. Another group of suitable solvents are the various acetates wherein the ester portion contains from 1 to about 5 carbon atoms with examples including methyl acetate, ethyl acetate, and the like. Various ketones having from about 3 to about 10 carbon atoms can also be utilized such as acetone, methyl ethyl ketone, and the like. Polymerization of the various urethane forming components such as the prepolymer components are carried out in the solvent at suitable temperatures using suitable catalysts to generally form a urethane prepolymer.

Solvent Route - Chain Extension [0125] Chain extension of the various urethane prepolymers generally utilizes hydroxyl terminated chain extenders known to the literature and to the art such as various organic diols or glycols having a total of from 2 to about 20 carbon atoms such as alkane diols, cycloaliphatic diols, alkylaryl diols, and the like. Alkane diols which have a total from about 2 to about 6 carbon atoms are often utilized with examples including ethanediol, propane glycol, 1 ,6-hexanediol, 1 ,3-butanediol, 1 ,5-pentanediol, neopentylglycol, and preferably 1 ,4-butanediol. Dialkylene ether glycols having from 4 to about 20 carbon atoms, can also be utilized such as diethylene glycol and dipropylene glycol. Examples of suitable cycloaliphatic diols include 1 ,2-cyclopentanediol, 1 ,4-cyclohexanedimethanol (CHDM) and the like. Examples of suitable alkylaryl diols include hydroquinone di(β-hydroxyethyl) ether (HQEE), 1 ,4-benzenedimethanol, bisethoxy biphenol, bisphenol A ethoxylates, bisphenol F ethoxylates and the like. Still other suitable chain extenders are 1 ,3-di(2-hydroxyethyl) benzene, and 1 ,2-di(2-hydroxyethoxy) benzene. Mixtures of chain extenders can also be utilized. [0126] The preferred hydroxyl-functional chain extenders of the present invention include 1 ,4-butanediol, ethylene glycol, diethylene glycol, 1 ,6-hexane diol, 1 ,4-cyclohexanedimethanol (CHDM), hydroquinone di(β-hydroxyethyl) ether (HQEE), and 1 ,4-benzenedimethylol. [0127] If an increase in molecular weight of the urethanes formed via a solvent route is desired, any residual isocyanate groups can be reacted with various diamines as set forth hereinabove with regard to the waterborne route such as EA, DETA, or TETA, and the like. Alternatively, multi-functional chain extenders can be utilized such as trimethylol propane, glycerol, pentaerythritol, 1 ,2,6-hexanetriol, N,N,N-triethano!amine, N,N-diethanolamine, trimethylolethane, and diethylenetriamine. Combinations of chain extenders can be utilized. The amount of multi-functional isocyanate components, e.g. multi-functional chain extenders, catalysts, and/or polyols utilized to form the polyurethanes is limited so that the polymer remains soluble and at a reasonable processing and handling viscosity.

Bulk Polymerization Route [0128] Another route to prepare the various thermoplastic urethane or urethane prepolymers is via bulk polymerization such as in a reaction vessel or an extruder. According to this route, the various urethane forming components such as the isocyanate reactive compounds, e.g. one or more polyols, one or more thiocarbonate compounds, one or more chain extenders, one or more functional modifiers, and the like are mixed together along with one or more isocyanates and heated to a suitable reaction temperature to form a thermoplastic polyurethane composition. [0129] Branched or precrosslinked urethane polymers are readily formed by utilizing polyisocyanates having 3 or 4 isocyanate groups and/or active hydrogen compounds such as the various above listed polyols having at least three functional groups such as a hydroxyl group thereon. Chain extenders and/or various dispersants can also be utilized having 3, 4 or more isocyanate reactive functional end groups. Such compounds are known to the art and to the literature. [0130] Thermoset or crosslinked polymers can be obtained by using multi¬ functional crosslinking agents customary in the industry, such as, for example, water-soluble or -emulsifiable melamine or benzoguanadine resins, low viscosity polyisocyanates, water-em ulsifiab Ie polyisocyanates or water-emulsifiable prepolymers having terminal isocyanate groups, water-soluble or -dispersible polyaziridines, poly-epoxy functional compounds, epoxy-silanes and blocked polyisocyanates, which can be added during formulation of water-dilutable coatings, adhesives and sealants using the polyacrylic-urethane dispersions according to the invention. Thermoplastic Polyurethanes and Formation Routes Thereof [0131] The thermoplastic polyurethanes of the present invention whether prepared via a waterborne dispersion, a solution or bulk polymerization can be conducted by several different routes which are briefly summarized and then more fully described. Polyurethanes are generally formed by reacting 1) one or more isocyanates; 2) one or more hydroxyl-terminated thiocarbonate compounds, polymers, or copolymers; 3) optionally, one or more isocyanate reactive polyols; 4) optionally, one or more chain extenders; and 5) optionally a catalyst. [0132] A prepolymer "one-shot" route can be utilized wherein a hydroxyl terminated thiocarbonate copolymer component containing repeat groups therein derived from a conjugated diene and/or a vinyl monomer, optionally a polyol, and optionally a dispersant, are reacted with a polyisocyanate optionally in the presence of a catalyst to form an isocyanate terminated prepolymer, which is subsequently chain extended. The polyurethane can either be solvent borne or waterborne. A second route relates to a polyurethane prepolymer made by using various conjugated diene and/or vinyl monomers as a diluent wherein the hydroxyl-terminated thiocarbonated compound, polymer, or copolymer component, optionally but desirably a polyol, a dispersant, a chain extender, and a catalyst are all added together, mixed, and polymerized. That is, all the various reactants can be added together and polymerized via a so-called "one-shot" process. The polymer can be neutralized and a dispersion formed. The vinyl and/or diene monomers are then reacted into the backbone of the thiocarbonate. A third route relates to reacting a polyol with a diisocyanate to form a prepolymer which is subsequently reacted with one or more thiocarbonate compounds to form a thiocarbonate end capped urethane block. Various vinyl monomers and/or conjugated diene monomers are then in situ polymerized to form block copolymers such as an ABA block copolymer, if desired. [0133] Regardless of the reaction route, various vinyl and/or conjugated diene monomers can exist as repeat units within the thiocarbonate compound before it is reacted; or be initially contained within the mixture, or subsequently added after formation of a dispersion and then reacted into the backbone of the thiocarbonate compound.

Prepolymer Route [0134] One polyurethane formation route involves a prepolymer route for preparing a urethane-acrylic copolymer dispersion utilizing a polyacrylate polyol prepared from a hydroxyl functional thiocarbonate compound previously described, an anionic dispersant, a polyisocyanate, and optionally a non-reactive organic solvent which can be utilized to control the viscosity of the prepolymer. In this route, all of the above desired ingredients are added to reaction vessel and reacted with a catalyst optionally being added with the above ingredients or after partial reaction thereof. The prepolymer is subsequently neutralized as by an amine followed by the addition of water. Chain extension can then be carried out. This route utilizes a hydroxyl-terminated thiocarbonate compound such as any of those set forth in Block Formulas AA, BB, CC, or EE where j equals 1 or 2 containing repeat groups derived from the one or more conjugated dienes and/or the one or more vinyl-containing monomers such as vinyl acetates. Preferred conjugated diene or vinyl compounds which can be utilized included styrene or an (meth)acrylate wherein the ester portion contains from 1 to about 10 carbon atoms such as ethylacrylate, butylacrylate, or 2-ethylhexylacrylate. [0135] Various solvents can be utilized with organic solvents being desired as noted above with N-methylpyrrolidone being preferred. [0136] Optionally, one or more active hydrogen or isocyanate reactive compounds such as a polyol can be utilized. Such polyols are set forth hereinabove with the hydrocarbon polyols, polyester polyols, polycarbonate polyols, and the polyether polyols such as tetramethyleneoxide polyol which is preferred. [0137] The isocyanate utilized to form a prepolymers is generally a diisocyanate as set forth hereinabove. Thus, generally any of the above-noted aliphatic polyisocyanates, the cycloaliphatic polyisocyanates, or the aromatic polyisocyanates can be utilized with the cycloaliphatic polyisocyanates being preferred such as dicyclohexylmethane diisocyanate and isophorone diisocyanate. [0138] The formation of the urethane-acrylic copolymer prepolymer is formed by combining the above-noted compounds and heating at an elevated temperature such as from about 300C to about 1000C and desirably from about 400C to about 900C. An excess of the polyisocyanate is preferably utilized for subsequent chain extension. If a waterbome dispersion has been formed, desirably amine type chain extenders are utilized whereas if the prepolymer was formed by solution polymerization, diol type chain extenders are utilized. During the prepolymer formation, a urethane catalyst can be utilized as noted hereinabove or optionally, the prepolymer reaction can be partially carried out at which time a catalyst such as a tin catalyst can be added. [0139] Once the urethane dispersion derived from a thiocarbonate-vinyl copolymer has been formed, it can be chain extended utilizing any of the above- noted chain extenders set forth herein with hydrazine being preferred. Alternatively, the chain extender can be contained in the water which is preferable with aromatic isocyanate based prepolymers. [0140] Various nuances of the above prepolymer dispersion route of forming a polyurethane derived from a thiocarbonate-acrylate copolymer can be utilized. For example, if a dispersion is not desired but only a solvent borne urethane thiocarbonate-acrylic polymer, a neutralizing agent and water is not utilized but only the above-noted solvents which are then required in additional amounts to control the viscosity of the final molecular weight of the composition. Another option is that if a pre-crosslinked polymer or copolymer is desired, it can be achieved by a number of ways such as by utilizing a polyol, or an isocyanate, or even a chain extender having a functionality of at least three, alone or in combination with a difunctional chain extender. Crosslinking can also be achieved by post addition of crosslinkers. [0141] The following examples with respect to the preparation of a polyurethane dispersion by essentially adding all of the components together serves to illustrate, but not to limit the present invention. [0142] A prepolymer was prepared by combining all of the ingredients below except the catalysts at 600C to a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The temperature of the reaction mixture was raised to 84°C-86°C and held at this temperature for 30 minutes. The catalyst was then added at 84°C-86°C and the temperature held there for another 1.5 hours or until theoretical NCO% was reached as indicated by titration of a small sample.

[0143] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 16.4 parts of triethylamine at 68°C to 700C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with hydrazine to give a 40.4% solids polyurethane dispersion with low sediment, a viscosity of 170 cps (at 25°C) at a pH of 7.5. [0144] The following is an example of the use of an acetone functional acrylic polyol prepared from ethyl acrylate and diacetone acrylamide using the RAFT diol (dithiocarbonate based) to prepare a self-crosslinking urethane-acrylic copolymer. [0145] A prepolymer was prepared by combining all of the ingredients below except the catalyst at 600C to a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The temperature of the reaction mixture was raised to 84°C to 86°C and held at this temperature for 30 minutes. The catalyst was then added at 84°C to 86°C and the temperature held there for another 1.5 hours or until theoretical NCO% was reached as indicated by titration of a small sample.

[0146] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 14.4 parts of triethylamine at 68°C-70°C and dispersing the neutralized prepolymer in water while maintaining the water/dispersion temperature below 28°C. The dispersed prepolymer was extended with hydrazine to give a 43.6% solids polyurethane dispersion with low sediment, a viscosity of 105 cps (at 250C) at a pH of 9.3. To this dispersion adipic acid dihydrazide (ADH) was added to render it self-crosslinking.

Prepolymer Route - "In-Situ" Acrylic Urethane Polymerization [0147] Another route with regard to the preparation of a urethane thiocarbonate-vinyl copolymer comprises mixing all the various reactant components together utilizing a conjugated diene and/or a vinyl monomer such as an acrylate as a diluent, desirably with a dispersant and optionally a polyol, and reacting the same with a isocyanate to form a polyurethane prepolymer. The composition is then neutralized with a tertiary amine if required, dispersed in water, and generally subsequently chain extended. Then, the diluent such as acrylate and/or styrene monomers are polymerized into the thiocarbonate unit utilizing a free radical initiator. This route permits the size of the thiocarbonate vinyl block to be tailor made, permits formation of uniform high molecular weight acrylate blocks, and desirable properties typically associated with acrylic polymers such as weatherability, resistance, adhesion, and flexibility with respect to a desired Tg. Moreover, this approach is more economical in that a separate polyol preparation step is not required and the monomer can act as a solvent for the prepolymer eliminating the need of processing solvents. [0148] The preparation of the polyurethane dispersion using various monomers such as conjugated dienes or vinyl containing monomers as a diluent is carried out utilizing many of the same components set forth hereinabove as well as in the immediately above described urethane prepolymer route and are hereby fully incorporated by reference. Hence the procedure will not be repeated herein. [0149] An essential reaction component of the present route is the utilization of a hydroxyl-terminated thiocarbonate discussed hereinabove such as those set forth in Formulas AA, BB, CC, and EE wherein j equals 1 or 2 and thus are fully incorporated by reference. As noted, these thiocarbonates desirably do not have any units derived from a conjugated diene or a vinyl monomer therein. [0150] An optional reaction component is an active hydrogen or isocyanate reactive compound such as the one or more polyols described herein above. Of these numerous components, the hydrocarbon polyols generally have a total of from 2 to about 12 carbon atoms and/or the two hydroxyl groups or a polyether polyol is utilized such as tetramethyleneoxide polyol. [0151] Since a polyurethane dispersion is made, either an ionic or nonionic dispersant is utilized with the above noted acid dispersants being preferred such as the dihydroxy-carboxylic acids. [0152] Rather than utilizing a solvent, various reactive monomers such as a conjugated diene monomer and/or one or more vinyl containing monomers such as the various acrylates are utilized as a diluent and the same can be subsequently polymerized into the polyurethane to form the urethane thiocarbonate-vinyl copolymer. These monomers are set forth hereinabove and are thus hereby incorporated by reference. The vinyl containing monomers are desired with a styrene type and the acrylates or methacrylates generally having from 1 to 18 carbon atoms in the ester portion being preferred. [0153] The above noted various types of polyisocyanates are utilized with diisocyanates being highly preferred such as the aliphatic polyisocyanates, the cycloaliphatic polyisocyanates, aromatic polyisocyanates, and the like with the cycloaliphatic polyisocyanates being highly preferred. [0154] The reaction of the various hydroxyl-containing components with the diisocyanates is carried out in a manner as set forth hereinabove utilizing suitable urethane catalysts such as the various tin catalysts described above. Naturally, an excess of the isocyanate is utilized so that the polymers substantially contain isocyanate end groups for subsequent reaction as by chain extending. [0155] In order to form a dispersion, the active groups of the ionic type dispersants are neutralized and thus with regard to an acid dispersion, the same are neutralized using various basic compounds as noted hereinabove such as the various tertiary amines, ammonium hydroxide, and the like. Generally neutralization is followed by or occurs simultaneously with addition of the neutralized polymer to water to form an aqueous dispersion of the urethane polymers. [0156] The various diluent monomers are then polymerized utilizing free radical initiators as noted hereinabove such as various peroxides, peroxyesters, and the like. An important advantage of the present route is that the urethane thiocarbonate-acrylate copolymers can be tailor made with regard to the size of the incorporated monomer such as styrene or an acrylate by the amount thereof utilized as a diluent versus the raft (thiocarbonate) diol. Uniform block copolymers of the styrene and/or the acrylate can thus be made. Hence, chemical and physical properties of the end copolymer can also be controlled such as hardness, solvent resistance, functionality, and the like. The polyurethanes can possess the advantages of acrylic polymers such as weatherability, adhesion and resistant properties. The diluent monomers when polymerized are incorporated into the thiocarbonate compounds between the sulfur atom and the adjacent group

R1 R5

C or the group —

R2 R4 An example of such is Block Formula AA as is set forth hereinabove. Naturally, a portion of the urethane copolymer will contain a structure as set forth in Block Formulas AA, BB, CC, and EE where j equals 1 or 2. Preferred diluent monomers include styrene, an alkylacrylate, or an alkylmethacrylate, wherein the alkyl has from 1 to about 16 carbon atoms such as ethylacrylate, butylacrylate, and the like. [0157] Nuances of the above general description of the preparation of a polyurethane dispersion utilizing various monomers as a diluent includes the utilization of adding additional conjugated diene and/or vinyl monomer before polymerization, or after dispersing the urethane prepolymer, particularly after chain extension. Thus, relatively low viscosity dispersions can be prepared and then a desired amount of additional conjugated diene and/or vinyl type monomer such as acrylate can be added to achieve desirable blocks within the thiocarbonate as well as to achieve desired end properties. Another nuance is that various crosslinking agents can be added either during or after chain extension to form a crosslinked solid product generally in the form of a particle. While not preferred, when a solvent borne urethane thiocarbonate-acrylic copolymer is desired, a dispersant is not utilized but rather one or more solvents which generally or preferably do not enter into the polymerization reaction. Such solvents are described hereinabove and include compounds such as various alkanes, acetone, aromatic hydrocarbons, alcohols, N-methylpyrrolidone, acetate amides such as dimethyl formamide, and the like.

Example [0158] A prepolymer was prepared by adding all of the ingredients below except the catalysts at 600C to a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The temperature of the reaction mixture was raised to 84°C-86°C and held at this temperature for 30 minutes. The catalyst was then added at 84°C-86°C and the temperature held there for another 1.5 hours or until theoretical NCO% was reached as indicated by titration of a small sample.

[0159] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 16.4 parts of triethylamine at 68°C-70°C and then dispersing the neutralized prepolymer in water using high speed stirring while maintaining the water/dispersion temperature below 28°C. With continued stirring the dispersed prepolymer was extended with hydrazine. Polymerization of the acrylic was effected by adding 0.3 parts of a 1% Fe (EDTA) solution, then adding 5 parts of a 2% erythorbic acid solution neutralized with triethylamine and subsequently adding 3 parts of a 3.5% t-butyl hydroperoxide solution and heating at 34°C-36°C. The resulting polymeric dispersion has a solids content of 46.5% with a low level of sediment, a viscosity of 100 cps (at 25°C) at a pH of 8.4.

Example [0160] The following is an example of the preparation of a "pure" urethane- acrylic copolymer (without other soft segment polyol based raw materials) using the RAFT diol and acrylic monomers to create the soft-segment for the polyurethane.

[0161] A prepolymer was prepared by charging all of the ingredients below to a 4 neck flask equipped with a thermometer, overhead stirrer and gas inlet. The temperature of the reaction mixture was raised to 84°C-86°C and held at this temperature for 30 minutes. The catalyst was then added at 84°C-86°C and the temperature held there for another 1.5 hours or until theoretical NCO% was reached as indicated by titration of a small sample.

[0162] A polyurethane dispersion was prepared by neutralizing the above prepolymer with 20.2 parts of triethylamine at 68°C-70°C and then dispersing the neutralized prepolymer in water using high speed stirring while maintaining the water/dispersion temperature below 28°C. With continued stirring the dispersed prepolymer was extended with hydrazine. Polymerization of the acrylic was carried out by adding 0.3 parts of a 1% Fe (EDTA) solution and 3 parts of a 3.5% t-butyl hydroperoxide solution, heating to 34°C-36°C and then adding 5 parts of a 2% erythorbic acid solution neutralized with triethylamine. The resulting polymeric dispersion has a solids content of 34.5% with a low level of sediment, a viscosity of 50 cps (at 25°C) at a pH of 7.5.

Thiocarbonate Capped Prepolymer Route [0163] Still another polyurethane formation route relates to forming various block copolymers such as AB or (AB)nA blocks containing at least one thiocarbonate or acrylic "A" block blocks as well as at least one urethane "B" block, where n is from 1 to about 20 and desirably from 1 to about 5. This route generally involves the reaction of at least one polyol and an anionic dispersant and an excess amount of a diisocyanate to form a polyurethane prepolymer, in the presence of a conjugated diene or vinyl monomer diluent. Subsequently, the urethane prepolymer is reacted with one or more of the hydroxyl terminated thiocarbonate compounds set forth in Formulas AA, BB, CC, and EE where j equals 1 or 2, preferably 1, to produce a polyurethane prepolymer generally having terminal thiocarbonate compounds containing no conjugated diene or vinyl repeat units therein. The prepolymer is then neutralized and dispersed in water. The various acrylate monomers can then be polymerized in situ into the terminal thiocarbonate compounds in the presence of free radical initiators to yield a block copolymer such as an ABA wherein A is the thiocarbonate-acrylate block and B is a polyurethane block. According to this route, the size and molecular weight of the various blocks can be tailor made to yield suitable desired properties, such as molecular weight, flexibility, and hardness. Other advantages include the use of neutralizing agents which are more user friendly in that they are less volatile and offensive than conventional neutralizing agents such as TEA. Still another advantage is that the urethane prepolymer containing one or more thiocarbonate end groups can be stored, transported, moved to another location, or to an end user, etc. and then one or more conjugated diene and/or vinyl monomers added thereto such as styrene or an acrylate and polymerized into the thiocarbonate compounds via in-situ free radical polymerization. Still another advantage of the thiocarbonate end group containing urethane prepolymer is that different processes are available. For example, significantly higher prepolymer and water temperatures with respect to the dispersion step can be utilized as well as extended dispersion time (virtually unlimited) without loss of isocyanate end groups due to water side reactions since, of course, there are no isocyanate groups. This route is also particularly advantageous for aromatic isocyanates that are harder to disperse and more reactive towards water and typically leads to problems with sediment or dispersion quality. Generally, the thiocarbonate capped prepolymer route yields increased productivity and process flexibility with less off-grade product.

Other Prepolvmer Routes [0164] Any of the above described preparation routes of course can be used in combination to attain particular results or combine the practical benefits of each. For example, an acrylic polyol can be prepared according to the first or prepolymer route and used as a component in the second or in-situ urethane preparation route for the synthesis of the copolymer. While the above three basic routes have been utilized with respect to preferred embodiments of the present invention, it is to be understood that any of the other routes can also be utilized.

Polvurethane - Molecular Weight [0165] The number average molecular weight of the polymerized thermoplastic polyurethanes of the present invention made by the various routes can broadly range from about 10,000 to about 2,000,000, desirably from about 20,000 to about 1 ,500,000, and preferably from about 40,000 to about 500,000, unless crosslinked. The overall equivalent ratio of all NCO groups to all OH groups, i.e. NCO/OH is generally from about 0.1 to about 10, desirably from about 0.4 to about 4 and preferably from about 0.8 to about 2.2.

Thiocarbonate Urethanes Having Curable Functional Groups [0166] The isocyanate terminated thiocarbonate urethane compounds are subsequently reacted with a compound having at least one functional group reactive with the isocyanate and also at least one curable functional group. Such compounds include the hydroxy alkyl (meth)acrylates, acrylic polyalkylene oxide derivatives, or allyl group containing compounds which are described hereinbelow. Accordingly, the isocyanate terminated thiocarbonate urethanes and compounds reactive therewith including a curable functional group are placed in a suitable reaction vessel preferably equipped with a mixing device. The curable thiocarbonate urethane compounds are formed utilizing generally the same reaction conditions used to form the isocyanate terminated thiocarbonate urethane described hereinabove and incorporated by reference. Stoichiometric amounts of the reactants are preferably utilized, although in some embodiments an excess of compounds including the curable functional group are utilized. The curable thiocarbonate urethane resulting from the reaction can be cured as described hereinbelow. Compositions including the curable thiocarbonate urethanes can also be formed including other components comprising reactive or non-reactive diluents, photoinitiators, plasticizers, thickeners, or pigments, or combinations thereof as described herein. [0167] (Co)polymers can be made in the form of aqueous dispersions by those methods known in the art. For example, unsaturated carboxylic acids can be polymerized into the backbone of the thiocarbonate compounds subsequently neutralized with amines or bases, and dispersed under agitation into water. Alternatively, other stabilization means such as cationic, nonionic, zwitterionic, or anionic can be used to drive water into the polymer dispersion. The dispersion can be made even in absence of polymerized dispersing agent through a high shear dispersion process. In this case, presence of external emulsifying agents will stabilize the dispersion.

Addition of Curable Functionality to Acid Terminated Thiocarbonate Compounds [0168] The thiocarbonate compounds are reacted with a monomer or other compound having at least one curable functional group and a second functional group capable of reacting with the carboxylic acid or other functionality present on the thiocarbonate compound. In some embodiments, the thiocarbonate compounds can have repeat units, i.e., derived from vinyl, diene, or other monomers, polymerized into the backbone thereof as described hereinabove, either before or after, preferably before, the curable functionality is introduced into the thiocarbonate compounds. [0169] In one embodiment, an esterification reaction is performed utilizing the carboxylic acid group containing thiocarbonate compound and a curable compound having a hydroxyl group reactive with the acid or other hydroxyl reactive functionality of the thiocarbonate compound. Hydroxy alkyl (meth)acrylates are utilized in some embodiments and generally have the formula:

H2C= C(R17)COOR18OH

wherein R17 is H or CH3, and wherein R18 is optionally substituted and is a linear, branched, or cycloaliphatic hydrocarbon having from about 1 to about 50 carbon atoms, with about 1 to about 4 carbon atoms preferred. Substitutents include, but are not limited to, heteroatoms, ether groups, aryl groups, cyano, and halogens. Examples of suitable hydroxy alkyl (meth)acrylates include, but are not limited to, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, and hydroxy butyl methacrylate. For example, 2-hydroxy ethyl acrylate can be incorporated into a dithiocarbonate compound as follows to produce a curable thiocarbonate compound:

S + HOCH2CH2O-C-CH=CH2

wherein R4, R5, R6, and R7 are defined hereinabove. [0170] The reaction to form the curable thiocarbonate compound is performed in a reaction vessel preferably equipped with a mixing or agitating device and a condenser. The reactants, preferably with an excess of the curable compound having a hydroxyl group are heated to a temperature of about 6O0C to about 1500C, with about 1000C being preferred. A catalyst, such as a metal alkoxide or tin compound, or an acid such as a strong Brόnstead acid or Lewis acid, or a combination thereof is optionally utilized in the reaction. Inhibitors such as MEHQ or BHT can also optionally, but preferably be utilized in the reaction. The reaction is continued for a predetermined amount of time depending on temperature and any catalyst utilized until complete. Oxygen is advantageously present to prevent spontaneous thermal polymerization. The reaction product is subsequently isolated if desired. [0171] In yet another embodiment, curable thiocarbonate can be prepared by reacting a carboxylic acid group containing thiocarbonate compound with an acrylic polyalkylene oxide derivative. The acrylic polyalkylene oxide derivatives have the general formula:

H2C= C(R17)CO(OCH2CH)nOH R19

wherein R17 is H or CH3 and R19 is H, CmH2m+i where m is 1 to about 50, or an aryl, and n is 1 to about 150 and preferably 1 to about 50. Specific examples include, but are not limited to, polyethylene glycol mono (meth)acrylate and polypropylene glycol mono (meth)acrylate. Polyalkylene oxide derivatives are available from lnspec Specialities as Bisomer® under such designations as PEM6E, PPA6, PPM5S, PPM6E and PEA6. The reaction conditions are generally the same as utilized in the hydroxy alkyl (meth)acrylate and thiocarbonate compound esterification reaction. [0172] Curable thiocarbonates are also prepared by reacting compounds having a polymerizable allyl group and also containing at least one functional group reactive with the carboxylic acid group thiocarbonate compound such as allyl amines, diallyl amines, and mono-, di- and other polyallyl alcohols, and allyloxy alcohols. The allyl containing compounds generally have the formula: R20, where n is 1 to about 10, with 1 to about 3 preferred; and wherein R20 is linear or branched, an aliphatic, aromatic, or araliphatic hydrocarbon, optionally containing heteroatoms, and/or at least one acid reactive functional group such as -NH2, -OH, or the like. Examples include, but are not limited to, allyl alcohol, allyl amine, allyl alcohol 1 ,2- butoxylate-block-ethoxylate, allyl alcohol propoxylate, 4-a!lyl-2,6-dimethoxyphenol, 2-allyl-6-methylphenol, 1-allyl-3-(2-hydroxyethyl)-2-thiourea, 3-allyl oxy-2-hydroxy-1-propanesulfonic acid salt, 3-allyloxy-1 ,2-propane diol, 2-allylphenol, trimethylolpropane allyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, allyl oxyethyl ether, diallyl amine, or diallyl bisphenol A. One example reaction mechanism is as follows: ° R C2H5 P-TsOH (CH2=CHCH2)2N-C-S -COOH + HOCH2- C-e CH2OCH2CH=CH2);? -H2O R R C 29Hπ5 (CH2=CHCH2)2N-C-S- -COOCH2 - C-f- CH2OCH2CH=CH2)2 R

[0173] In a further embodiment, the carboxylic acid terminated thiocarbonate compounds are reacted with an epoxy group containing compound bearing a curable functional group. Various epoxy group containing compounds are known to the literature and to the art and generally have one of the following formulae:

H2C= C(R17)COOR19- CH-CH2,

H2C- CHCH2OCH2 — C ΛH-CH2

wherein R17 is defined above, and wherein R19 is an alkylene group or ether group(s) having from 1 or 2 to about 50 carbon atoms with about 1 to about 10 carbon atoms preferred. Specific examples of suitable epoxy group containing compounds include, but are not limited to, glycidyl methacrylate, allyl glycidyl ether, 4-vinylcyclohexane epoxide, and glycol acrylate. [0174] In order to form the curable thiocarbonate compound having at least one unsaturated terminal group, the acid terminated thiocarbonate compound, epoxy group containing compound, and a suitable catalyst, i.e., a metal salt such as zinc chloride, zinc acetate, a Lewis acid, or a phosphonium salt such as tetrabutyl phosphonium bromide, or a phosphine such as triphenyl phosphine are added to a reaction vessel, preferably equipped with a mixing or agitating device and a condenser. An inert atmosphere such as nitrogen is preferably utilized and the reactants are subsequently heated to induce reaction to a temperature generally from about 4O0C to about 125°C and preferably from about 6O0C to about 9O0C until the reaction is completed to produce a curable thiocarbonate compound having at least one unsaturated terminal group. [0175] An example reaction mechanism for producing a curable thiocarbonate compound derived in part from an epoxy group containing compound, in this case allyl glycidyl ether, bearing a polymerizable unsaturated functional group is as follows:

wherein R4, R5, R6 and R7 groups have been described hereinabove. [0176] A further example of a reaction scheme for forming a thiocarbonate compound having unsaturated terminal groups derived from an unsaturated group containing epoxy compound is as follows:

RE N- C- H2

wherein R4, R5, R6 and R7 groups have been described hereinabove.

Example of Dithiocarbonate Polymers Having Repeat Units Derived from Butyl Acrylate and Unsaturated Terminal Groups Derived From an Epoxy (Meth)Acrylate [0177] The following non-limiting example illustrates the formation of a thiocarbonate polymer having repeat units derived from butyl acrylate (BA) monomers reacted with glycidyl methacrylate to produce a radiation curable thiocarbonate polymer having two unsaturated end groups.

[0178] The dithiocarbonate polymer having butyl acrylate repeat units is formed in a first step via RAFT polymerization. In a 100ml, 3 port reaction vessel equipped with mechanical stirrer, oilbath, j-chem thermocouple unit, and a condenser, 3.4 grams of thiocarbonate compound, 25 grams butyl acrylate, 0.01 gram 2,2'-azobisisobutyronitrile (AIBN) catalyst, 25 ml dimethylformamide were added and placed under a nitrogen atmosphere. The reactants were heated to about 800C until an exotherm reaction took place. Once the butyl acrylate had been polymerized, 3.41 grams glycidyl methacrylate and 0.05 gram triphenylphosphine catalyst were added and the reaction mixture was subsequently heated to about 1000C under the nitrogen blanket for a period of about 3 hours until the reaction was complete. The reaction product, the dithiocarbonate polymer having terminal unsaturation, was confirmed by GPC.

Curable Compounds Derived From Hydroxyl Terminated Thiocarbonates [0179] In a further embodiment, curable thiocarbonate compounds are prepared from the hydroxyl terminated or pendant hydroxyl group containing thiocarbonate compounds or a combination thereof. As described hereinabove, the hydroxyl terminated thiocarbonate compounds are generally prepared by reacting a polyol with the acid group containing thiocarbonate compounds, or the isocyanate terminated thiocarbonates described herein, or other thiocarbonate compounds having a functional group reactive with the polyol. The hydroxyl groups present on the thiocarbonate compounds can be further reacted with generally any carboxylic acid containing a curable functional group such as an unsaturated group. Examples of suitable acids include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, allylic acid, itaconic acid, maleic acid, fumaric acid and styrene sulfonic acid. The reaction conditions are generally the same as described hereinabove for reaction of the acid containing thiocarbonate compounds with a hydroxyl group containing compound bearing a curable polymerizable functional group.

Curable Backbone Functionality [0180] Curable functional groups such as unsaturated functionality can also be tethered to the backbone of the thiocarbonate compounds instead of or in addition to being present as one or more of the thiocarbonate terminal groups, if desired. In one embodiment, one or more, same or different polymerizable monomers bearing an acid or alcohol functional group is polymerized into the thiocarbonate compound. Subsequently, the functional group is reacted with a polyfunctional compound reactive therewith also containing a curable functional group(s). For example, hydroxy alkyl (meth)acrylate monomer(s) or an unsaturated diol such as trimethylol propane mono (meth)acrylate or combinations thereof, are polymerized into the backbone utilizing the RAFT polymerization method described herein. The hydroxyl functional groups which are pendant from the thiocarbonate compound are then utilized in an esterification reaction as described hereinabove, for example, utilizing (meth)acrylic acid, which results in the thiocarbonate polymer having pendent unsaturated chain ends. As a further example, acrylic acid is polymerized into the backbone of the thiocarbonate compound with the carboxylic acid group then subsequently reacted with an alcohol having a curable functional group present thereon, such as a hydroxy alkyl methacrylate. In a further embodiment, a compound containing a curable functional group, such as allyl (meth)acrylate is directly polymerized into the thiocarbonate compound to provide pendent curable functionality to the thiocarbonate compound.

Curable Compositions [0181] The thiocarbonate compounds having a curable functional group such as an unsaturated end group can be cured utilizing for example radiation, thermal, radical, or oxidated curing, or combinations thereof. In addition to the thiocarbonate compounds, the curable compositions can include additional curable diluents, i.e. monomers, oligomers, or polymer, or photoinitiators, or other desired additives as known in the art. [0182] Dual cure compositions can also be formed utilizing the curable thiocarbonate compounds of the present invention. Such dual cure compositions have the advantage of crosslinking the polymer in shadow areas where radiation cannot reach polymerizable monomers, oligomers or polymers. By way of non- limiting example, (meth)acrylic acid and hydroxy alkyl acrylate monomers are incorporated into the thiocarbonate compound backbone via (RAFT) polymerization. Pendant functional groups of the polymerized monomer can be sites for additional thermal curing after the UV or other radiation induced polymerization curing step or other curing mechanism is applied. Epoxy resins, carbodiimide, alkoxysilanes, ethylene urea, or isocyanates, or the like can be additional parts of the thermal curing system. [0183] In a further embodiment of the present invention, radiation curable compositions are formed comprising a radiation curable thiocarbonate compound having at least one radiation curable functional group, preferably an unsaturated group and at least one thiol group containing compound. Any of the radiation curable thiocarbonate compounds described herein can be utilized in the thiol thiocarbonate curable compositions. Crosslinked networks can be formed from polythiols and radiation curable thiocarbonate having two or more curable functional groups per compound. High quality coatings having many applications such as in the electronic and packaging industries can be formulated. [0184] The thiols suitable for use in the present invention compositions have the formula: R ~{SH)n wherein R21 is optionally substituted and is a linear or branched alkyl, aryl, or araliphatic, wherein the substituents can be heteroatoms such as oxygen. [0185] Examples of such thiols include, but are not limited to, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), and trimethylolpropane tris(2- mercaptoacetate) . [0186] The thiol thiocarbonate curable composition is generally cured in the presence of ultraviolet light. In some embodiments the compositions include an initiator as described herein. Various other additives, diluents, etc. can be utilized in initial embodiments as also described. It is believed that during UV curing, the thiol group reacts with the radiation curable group of the thiocarbonate compound, forming a linkage there between.

Radiation Curable Compositions [0187] The above described thiocarbonate compounds having a radiation curable functional group such as an unsaturated end group can be exposed to a radiation source such as ultraviolet light or an electron beam and cured. The thiocarbonate compounds having a curable functional group can be cured alone generally utilizing relatively higher amounts of energy due to the thiocarbonylthio group present therein. In additional embodiments, other radiation curable diluents, i.e., monomer(s), oligomer(s) or polymer(s); or photoinitiators; or combinations thereof, can be co-cured with the radiation curable thiocarbonate compound. [0188] The optional photoinitiators utilized in the present invention are radiation or light- excited compounds that photolyze directly or indirectly into free radicals or cations which cause polymerization to occur, very rapidly in most cases. Numerous types of photoinitiators are known. One type of photoinitiator when irradiated with the radiation source is taken from a ground state to an excited state and generates free radicals capable of initiating polymerization. Occasionally, a polymer or a composition containing polymers which will not directly interact with the excited photoinitator chosen and a synergist, such as a tertiary amine which interacts with the excited photoinitiator by means of electron transfer and hydrogen abstraction is utilized. Other synergists commonly utilized include amides, urea, alcohols and ethers that contain a hydrogen atom on the carbon position alpha to the alcohol oxygen or ether oxygen, and thiols that have a hydrogen attached to the sulfur atom. Other photoinitiators which are utilized in some embodiments are homolytic or intramolecular fragmentation type photoinitiators. When exposed to a radiation source the photoinitiator is raised to a light-excited state. Then the excited compound undergoes a spontaneous, intramolecular photocleavage to produce two radicals, both of which are capable of initiating photopolymerization. Homolytic fragmentation photoinitiators are inhibited by the presence of oxygen and therefore an inert atmosphere is preferably utilized such as nitrogen, carbon dioxide, or argon. [0189] Examples of suitable photoinitiators include, but are not limited to, benzophenone, 9,10-anthraquinone, benzil, 2-chlorothioxanthone, p- diacetylbenzene, 2,3-diethylthioxanthone, dodecylthioxanthone, ethylhexyl p- dimethylamino benzoate, fluorenone, 2- or 4-isopropylthioxanthone, 2-methyM-[4- (methylthio)phenyl]-2-morpholino-propanone-1 , 4,4'bis(N,N'-dimethylamino) benzophenone, 4-phenylbenzophenone, quinone, 9,10-phenanthrenequinone, thioxanthone, 2,4,6-trimethylbenzophenone/4-methylbenzophenone blend, acetophenone, 2,2-diethoxyacetophenone (DEAP), 2,2-dimethoxy-2- phenylacetophenone, 2,2-dimethyl-2-hydroxyacetophenone, 2-ethoxy-2- isobutoxyacetophenone, 1-hydroxycyclophenyl phenyl ketone, benzyl alkylketals, benzoin, benzoin alkyl and aryl ethers, isobutyl benzoin ether, benzoin thioethers, halogenated acetophenones, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1-phenyl-1,2-propanedione-2-benzoyloxime, or combinations thereof. Preferred photoinitiators are benzophenone, 4,4'bis(N,N'-dimethylamino) benzophenone and 4-phenylbenzophenone. Photoinitiators are commercially available from sources such as Ciba Specialty Chemicals as lrgacure 184, lrgacure 369, lrgacure 500, lrgacure 651 , lrgacure 784, lrgacure 819, lrgacure 907, lrgacure 1000, lrgacure 1300, lrgacure 1700, lrgacure 1800, lrgacure 1850, lrgacure 2959, Darocur BP, Darocur 1173 and Darocur 4265, and Ebecryl BPO® from UCB Chemicals. When utilized, the photoinitiator is present in an amount generally from about 0.1 to about 10 parts and preferably from about 0.5 to about 5 parts per 100 parts dry weight of radiation curable compounds present, i.e., radiation curable thiocarbonate and optional other radiation curable monomers, oligomers, or (co)polymers. [0190] As stated herein, the curable compositions of the present invention can optionally include other curable diluents such as monomers, oligomers, or (co)polymers. Examples include, but are not limited to, diacrylates, triacrylates, acrylated epoxy oligomers, acrylated urethane oligomers both aromatic and aliphatic, polyester oligomers including acrylate polyester oligomers, acrylated acrylic oligomers, cycloaliphatic and epoxide resin. Specific examples of curable monomers include, but are not limited to, 1 ,4-butanediol diacrylate, 1 ,3-butylene glycol diacrylate, diethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, 1 ,6-hexanediol diacrylate, neopentyl glycol diacrylate, poly(ethylene glycol)200 diacrylate, poly(ethylene glycol)400 diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glyceryl triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, pentaacrylate ester, pentaerythritol tetraacrylate, ethoxylated trimethyolpropane triacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, trimethyolpropane triacrylate, trimethyolpropane trimethacrylate, triallylether, triethylene glycol divinyl ether, triallyltriazene, pentaerythritol tetraacrylate and ethylene glycol dimethacrylate. [0191] The compositions of the present invention, in addition to the above- identified components can also contain various non-radiation curable monomers or (co)polymers such as monoacrylates, additives, fillers, lubricants, UV stabilizers, plasticizers, nanoparticles of oxides (Siθ2, N2O3, etc.) and clays, e.g. waxes, antioxidants, thickening agents, surfactants, and the like. The additional optional components can be utilized in conventional amounts as known to the art and to the literature. For example, suitable fillers include talc, silicates, clays, calcium carbonate, and the like. [0192] If it is desired that the polyurethane compositions of the present invention have a color or hue, any conventional pigment or dye can be utilized in conventional amounts. Hence, any pigment known to the art and to the literature can be utilized as for example titanium dioxide, iron oxide, carbon black, and the like, as well as various dyes provided that they do not interfere with the crosslinking reactions. [0193] The radiation curable thiocarbonate compound containing compositions of the present invention are cured by exposing the composition to a radiation source as described hereinabove, such as ultraviolet light radiation or an electron beam, etc. UV curing generally takes place at a wavelength of about 160 Nm to about 400 Nm. Intensity of the radiation will depend upon the speed of the substrate and time of exposure as known to those skilled in the art.

Applications [0194] Before curing, the composition can be applied to any desirable substrate or backing including, but not limited to, wood, plastic, metal, paper, fabric, and concrete. The radiation source is applied for a suitable period of time to produce the desired degree of curing. Uses for the compositions of the present invention comprise overprint varnishes for paper; adhesives; clear coats; inks; sealants; caulking; coatings for fiber optics, printed circuits, and audio and video discs; dental fillings; and pressure sensitive adhesives. [0195] The curable thiocarbonate compositions can be used to coat fabrics, or other substrates such as adhesive laminates or coatings. Suitable fabrics can be either woven or non-woven and made from polyester fibers, polyolefin fibers, nylon fibers or other synthetic fibers, or natural fibers such as cotton wool, or the like, or combinations thereof and the like. Industrial applications include coated films, sheets, or fabrics as for conveyer belts, containers, collapsible storage bags (e.g., fuel, water, fruit juices, food oils, heating oils etc), inflatables (e.g., escape slides and platforms, floatation devices, air-mattresses, life jackets, white-water or life rafts, oil booms, petro-seals, power lifting devices, weather balloons) or grape press membranes, and the like. In the apparel industry, uses include labels and stickers used in laundry and professional outfits, as well as protective clothing/apparel, protective covers, rainwear, sealable coatings for labels, surgical drapes, protective apparel, synthetic leather, tents, upholstery, wet or diving suits, and the like. Other uses include liners for pipe repair, load space covers, and the like. [0196] The curable compositions can also be used to make unsupported film and sheet for example via extrusion or calendering. Applications for such films and sheets include air mattresses, shower curtains, aeration sheets for water purification plants, adhesives, equipment covers, protective wear, aprons, body bags, tank liners, pipe liners, and the like. The curable compositions can be formed into articles comprising films, membranes or sheets of any desired thickness and range generally from about 0.25 or about 0.50 mils to about 10 mils (about 6.35 or about 12.7 to about 254 micrometers), and preferably from about 1 mil to about 4 mils (about 25.4 to about 101.6 micrometers).

Example of Radiation Cured Thiocarbonate Compositions [0197] A radiation curable dithiocarbonate urethane compound having two unsaturated terminal groups was prepared as follows. In a first step, a dithiocarbonate polymer having hydroxyl end groups and repeat units derived from butyl acrylate was prepared as shown in the below reaction mechanism.

[0198] The polymerization reaction was performed in a 3000 ml, 3 port reaction vessel equipped with a mechanical stirrer, an oilbath, a thermocouple unit and condenser. The reactants, 0.5736 moles of thiocarbonate compound, 8.7462 moles of butyl acrylate, 300 grams pentyl acetate, and 0.0021 moles of 2,2'-azobisisobutyronitrile (AIBN) were added to the vessel, placed under a nitrogen blanket and heated to about 800C for a period of about 5 hours to complete the reaction. [0199] The hydroxyl terminated dithiocarbonate compound having repeat units derived from butyl acrylate was subsequently reacted with a diisocyanate, isophorone diisocyanate (IPDI) to produce an isocyanate terminated polymer. 120.6 grams of the hydroxyl terminated dithiocarbonate and 19.6 grams isophoronediisocyanate were added to a reaction vessel and heated to a temperature of about 1050C for about 1.5 hours. Afterwards, .0059 grams BHT was added, and then 9.7 grams of hydroxy ethylacrylate was gradually added over about 1.5 hours to the reaction vessel to incorporate unsaturated end groups onto the isocyanate terminated dithiocarbonate. 20 minutes after the HEA was added, a drop of tin octoate catalyst was added to the reaction vessel and the reaction continued. After 1 hour reaction mixture had no residual NCO as determined by IR spectroscopy. GPC results showed that the thiocarbonate polymer had a Mn of about 4900. This composition was utilized in radiation curable composition 1 described hereinbelow. A second curable thiocarbonate composition having unsaturated terminal groups was prepared utilizing the above described method except that the tin octoate catalyst was added before the hydroxy ethylacrylate. The GPC results show that the thiocarbonate polymer had a Mn of about 6900. This composition was utilized in radiation curable composition 2 described in Table I. [0200] The radiation curable thiocarbonate compounds having unsaturated terminal groups were mixed with an additional radiation curable monomer, trimethylolpropane ethoxytriacrylate from UCB (Composition 1) or solvent, methyl ethyl ketone (Composition 2) and a photoinitiator, Darocur 4265 from Ciba Specialty Chemicals in various amounts to form radiation curable compositions. The amounts of the various components of the radiation curable compositions were as follows in Table I.

TABLE I Radiation Curable Composition 1 Radiation Curable Dithiocarbonate 30.50 grams TMPEOTA 15.2 grams Darocur 4265 2.29 grams Total Weight 47.99 grams Radiation Curable Composition 2 Radiation Curable Dithiocarbonate 36.50 grams MEK 12 grams Darocur 4265 1.83 grams Total Weight 50.33 grams

[0201] Each radiation curable composition was separately exposed to ultraviolet light under a nitrogen blanket. The ultraviolet source utilized was a 100W GE mercury bulb H100A4/UV. The radiation curable component 1 turned into a solid film after about 2 minutes. Radiation curable component 2 turned into a rubbery film after 30 minutes ultraviolet exposure. Radiation curable composition 2 does not contain any radiation curable component or diluent in addition to the dithiocarbonate compound. The experiment illustrates that the thiocarbonate alone is curable, without the need for any additional reactive diluents. [0202] 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.