WO2003002621A1

WO2003002621A1 - Radical polymerization of vinyl halide

Info

Publication number: WO2003002621A1
Application number: PCT/US2002/020588
Authority: WO
Inventors: Virgil Percec; Anatoliy V. Popov
Original assignee: University Of Pennsylvania
Priority date: 2001-06-27
Filing date: 2002-06-27
Publication date: 2003-01-09

Abstract

A living polymerization process for preparation of poly(vinyl chloride) (PVC) with controlled molecular weight and molecular weight distribution is described. The polymerization reaction can be initiated by various polyhalocarbon initiators in conjunction with non-metallic reducing single electron transfer reagents as catalysts and accelerated by electron shuttles. The process occurs at room temperature in water or water-organic solvent medium. The polymerization provides PVC with a controlled molecular weight and narrow molecular weight distribution. The halogen containing polymer compositions are useful as, among others, viscosity modifiers, impact modifiers and compatibilizers.

Description

RADICAL POLYMERIZATION OF VINYL HALIDE

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation in part of related application Serial No. 09/893,201 filed June 27, 2001 , which claims the benefit of U.S. Provisional Application 60/278, 1 14 filed March 23, 2001 .

BACKGROUND OF THE INVENTION

1.Field of the Invention

The present invention relates to the non-metal catalyzed radical and living radical polymerization of halogen containing monomers such as vinyl halides and vinylidene halides. In particular, this invention relates to a process for the synthesis, in the presence of a non- metallic catalyst, of poly(vinyl chloride) (PVC) with controlled molecular weight and narrow molecular weight^' distribution. The polymerization can be initiated from various electron accepting radical precursors such as polyhalocarbons in the presence of non-metal reducing single electron transfer reagents as catalysts which can include low valent sulfur salts containing S0₂ group. The process can be accelerated by electron shuttles such as alkyl viologens.

2. Description of the Prior Art

Heretofore, it was known to polymerize vinyl chloride (VC) and other vinyl halide monomers using conventional free radical processes. However, even in the presence of certain molecular weight additives, there is limited control over the molecular weight and polydispersity of the resulting polymer. In addition, VC polymers are thermally unstable and require thermal stabilizers for their practical use. Heretofore, there have been no methods reported to prepare poly(vinyl chloride) by a non-metal-catalyzed living process initiated from an active halide compound in which the molecular weight and the molecular weight distribution of PVC could be controlled.

Conventional free radical polymerization of vinyl chloride (VC) is accompanied by the formation of thermally labile tertiary and allylic chlorine defects which are responsible for the low thermal stability of poly(vinyl chloride). This provides its most relevant technological limitations. These structural defects are generated during the conventional radical polymerization of VC and are responsible for the initiation of a zipper mechanism of thermal degradation of PVC.

In U.S. Patent Serial No. 09/893,201 , which is herein fully incorporated by reference, there is described a process for the living radical polymerization of vinyl halides utilizing a metal (preferably Cu) catalyst. The polymerization processes taught therein include both non-aqueous high temperature and aqueous room temperatures processes. The former gives polymers with low yields (maximum 30%) and high molecular weight distribution up to about 1 .7. The latter achieves high conversions and lower molecular weight distribution (up to 1 .50). Both processes show linear molecular weight dependence on the monomer conversion. A single electron transfer mechanism mediated by metals is proposed for the initiation and dormant species activation steps

The PVC obtained by aqueous room temperature copper- catalyzed living radical polymerization of vinyl chloride as described in U.S. Patent Serial No. 09/893,201 , contains a vanishingly small amount of carbon-carbon double bonds in comparison with conventional PVC. This allows us to consider such a polymer as one free of at least allylic chlorine defects that could lead to new properties. Alternatively, the use of heavy metal in polymerization processes requires an additional utilization of the spent catalyst and purification of the polymer, thereby increasing the cost.

Previously, attempts on living radical polymerization of vinyl halides, which did not involve metal catalysis, were based on degenerative chain transfer processes using iodine containing chain transfer agents and peroxy-esters as initiators. As is taught in U.S. Patent 5,455,31 9, such a process was carried out at temperatures conventionally used for vinyl halide polymerizations. In addition, the polydispersity never decreased to values below 1 .7

SUMMARY OF THE INVENTION

There has now been found a process for the polymerization of vinyl chloride to form PVC polymers, and not telomers, utilizing a metal-catalyzed radical and living radical polymerization. Various activated mono, di, tri and multifunctional organic halide initiators, including the allylic chlorines normally found in chlorine containing polymers such as PVC, in conjunction with certain metal catalysts, can successfully initiate the radical polymerization of vinyl chloride. Optionally, a solvent or water or mixtures thereof and a ligand for the metal catalyst can be utilized in the polymerization of the vinyl chlorine monomer of the present invention. In a further embodiment, a method of polymerizing vinyl chloride to form PVC polymers, and not telomers, has now been found utilizing non-metal-catalyzed radical and living radical polymerization. Various activated electron accepting radical precursor initiators, such as polyhalocarbons, in conjunction with certain non- metallic single electron donors as catalysts can successfully initiate the radical polymerization of vinyl halide. The process occurs in water or aqueous - organic solvent solutions. Optionally, an electron shuttle such as an alkyl viologen, a surfactant, and a buffer can be utilized in the polymerization of the vinyl halide monomer of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the metal-catalyzed polymerization of chlorine containing monomers, appropriate initiators include halides and pseudohalides of the formula R-X, where R having from 1 to 100,000 carbon atoms, contains an activating electron withdrawing group such as cyano, ester, perfloroalkyl or any other unit capable of stabilizing a radical such as benzyl or allyl, and X = halide. The halide initiators include, but are not limited to various activated mono, di, tri and polyfunctional α,α -dihaloalkanes, ,α,α-trihaloalkanes, perhaloalkanes, perfloroalkyl halides, benzyl halides, allyl halides, sulfonyl halides, -haloesters, α-halonitriles, α-haloketones, imidyl halides, or combinations thereof. Additionally, any compound having labile carbon-halide, nitrogen-halide, sulfur-halide, phosporus-halide, silicon-halide bonds which can dissociate homolytically by themselves or in the presence of a metal catalyst are suitable for use as initiators in the present invention. Suitable structures for initiators utilized in the present invention are set forth in Scheme 3. Generally, preferred initiators include chlorine, bromine and thiocyanate containing compounds, with iodide initiators being desirable. Mono, di and trifunctional α-haloesters act as active initiators for the polymerization of vinyl chloride in the presence of Fe(0), TiCp₂CI₂ and Cu(0) and its salts such as Cu₂Te, Cu₂Se, Cu₂S, Cu₂0, CuCI, CuBr, Cul and copper thiophenoxide (CuSPh), copper butanethiolate (CuSBu), copper phenylacetylide (CuC = CPh). Various chlorine containing initiators such as CH3CH(CN)CI, CI-CH₂-Ph-CH2-CI or R-CH = CH-CH₂-CI and R-S0₂-Cl also promote the polymerization of chlorine containing monomers in the presence of catalysts such as Cu(0) and its salts, Fe(0) and TiCp₂C|₂. The preferred initiators that lead to polymers of narrowest molecular weight distribution in the presence of Cu(0) and its salts or complexes are the active iodine containing substrates of the type RιR₂R₃C-l where at least one of the R substituents is an electron withdrawing group (EWG) or radical stabilizing group such as benzylic, allylic, -halo, -cyano, -ester, - trifluoromethyl and so on. The other R substituents can be H, alkyl chains including polymer chains, electron withdrawing groups and combinations thereof. The preferred iodine containing initiators include: l-CH₂-Ph-CH₂-l, CH₃-CH(CI)-I, CH₂|₂, CHIs, C , CH₂ = CH-CH₂-I, CF₃-(CF₂)π-l, l-CH₂-CONH₂ and l-CH₂-COO-(CH₂)_n-H (n = 1 -20).

I

CH₃0-^ >-S0₂CI

X-CH₂- -CH₂-X

Scheme 3. Selected examples of initiators for the metal catalyzed radical polymerization of vinyl chloride

The amounts of such halide initiators utilized depend on the desired molecular weight of the halide containing polymer and are generally from about 5,000 to about 10, desirably from about 1000 to about 25, and preferably from about 500 to about 50 moles of halide containing monomer per one mole of initiating group. Generally the number average molecular weight of the halide containing polymer will be from about 500 to about 100,000, desirably from about 1000 to about 60,000, and preferably from about 3,000 to about 40,000.

The chlorine-containing monomers which are polymerized or copolymerized according to this invention are vinyl chloride and its structurally related derivatives and monomers known to copolymerize via a radical mechanism with vinyl chloride, including vinylidene chloride and 2-chloropropene. The preferred carbon atom range of each group of monomers is from 2 to 20. The copolymer can have a comonomer content from 1 % up to 99%, depending on the reactivity ratios of the comonomers used.

A metal species is utilized to catalyze the initiation reaction and continue the growth of the polymer chain. Typical radical forming catalysts include metal-based catalysts, as metals and/or salts thereof. Examples of such catalysts include metals in their zero oxidation state such as copper, iron, aluminum, cadmium, zinc, samarium, chromium, molybdenum, manganese, tungsten, cobalt, nickel, rhodium, ruthenium, palladium, titanium and certain higher valence salts thereof. The preferred catalyst will be dependent upon the initiator utilized and on the reaction media (such as solvent or water) and temperature. While the initiation step (addition of the radical fragment derived from the initiator to vinyl chloride) may be achieved with all catalysts, it is preferred that the metals be in their zero oxidation state for the metal catalyzed propagation and therefore, living radical polymerization to occur. Additionally, the catalyst may be a mixture of two or more metals in their zero oxidation state, a metal salt or complex, a mixture of two or more metal salts or complexes, or a mixture of two or more metals in their zero oxidation state with metal salts or complexes. Preferred catalysts include Cu(0), copper sulfide (Cu₂S), copper selenide (Cu₂Se), copper teluride (Cu₂Te) copper thiophenoxide (CuSPh), copper butanethiolate (CuSBu), copper phenylacetylide CuC = CPh, Fe(0), and titanium cyclopentadienyl dichloride (TiCp₂CI₂).

It has been found that Cu(O) is able to generate polymers regardless of the nature of the halide in the initiator. When Fe(0) is used as catalyst for the polymerization of vinyl chloride, it has been found that chlorine and bromine based initiators are suitable. The preferred initiators for Fe(0) are for example, the active (CH₃)₂(COOEt)-Br, CH₃-CH(Ph)-Br, F-Ph-S0₂-Cl, as well as the -CH₂- (CH₃)C(COOMe)-CI chain end of PMMA synthesized by metal catalyzed living radical polymerization. For titanium-based catalysts such as TiCp₂CI₂, chlorine containing initiators such as CI-CH₂-Ph-CH₂- Cl and CH₃CH(CN)-CI or CH₂ = CH-CH₂-CI are particularly suitable.

The amount of catalyst is dependent upon the desired reaction rate. Generally, the amount of catalyst will be from about 0.01 to about 10 desirably from about 0.75 to about 4, and preferably from about 1 to about 3 moles per mole of halide in the initiator.

A ligand can optionally be included in the polymerization reaction in order to aid in the solubilization of the catalyst. The ligand used will depend specifically and uniquely on the type of catalyst, the temperature of the reaction and on the reaction media such as solvent or water. The ligand can be any organic species capable of complexing the metal in its zero oxidation state and in its higher oxidation states. For Cu-based catalysts, the ligands can include basic aromatic and aliphatic nitrogen and phosphorus containing compounds such as 2,2'-bipyridyl (bpy) and its 4,4'-alkyl substituted compounds such as 4,4'-dinonyl-2,2'-bipyridyl (bpy-9), pentamethylene diethyl triamine, (PMDETA), tris(2-aminoethyl)amine (TREN), tris[2-(dimethylamino)ethyl]amine (Mee-TREN), triphenylphosphine, triphenylphosphine oxide, and combinations thereof. The foregoing ligands and 1 , 10-phenantroline are also appropriate for Fe-based catalysts. In addition, other ligands such as CO, acetylacetonate, or terpyridine may be used. The use of a ligand is not necessary for TiCp₂CI₂ but is preferred for Cu and Fe based catalysts.

When the optional ligand is present, the mixture will usually contain from about 0.1 to about 10 moles of ligand per mole of catalyst, desirably from about 0.75 to about 3 moles of ligand per mole of catalyst, and preferably from about 1 to about 2 moles of ligand per mole of catalyst.

Additionally, various additives may optionally be utilized in the polymerization. Depending on their structure, these additives may affect the molecular weight and molecular weight distribution of the resulting polymer. Such additives can include sodium iodide, urea, AI'Bu3, Ti(0Bu) and 2,6-di-tertbutyl-4-methyl pyridine, with 2,6-di- tertbutyl-4-methyl pyridine being preferred and may be added in a similar molar amount as the initiator.

Polymerization of the chlorine containing monomer is usually carried out in the presence of the catalyst and initiator in a closed vessel in an inert atmosphere such as nitrogen, or argon; under autogenous or artificially-induced pressure. The temperature of the polymerization can vary widely depending upon the type of initiator and/or catalyst, but is generally from about 0°C to about 180°C, desirably from about 10°C to about 1 50°C and preferably from about 20°C to about 130°C. It has been found that lower temperatures, i.e., 20°C - 90°C, depending on the initiator and catalyst system, lead to lower reaction rates, and higher molecular weight polymers. For solution polymerizations, the Cu(0)/bpy catalyst in conjunction with the X-CH₂-Ph-CH₂-X (X = Cl, Br, I, SCN) or CHb and Cl₄ initiators are effective only at about 1 20°C and above, while other chlorine, bromine and iodine based initiators generate polymers at temperatures as low as 60°C. This temperature is enough to allow the metal catalyzed reinitiation from chain such as -CH(CI)-X (X = I, Br, Cl). Higher temperatures promote an increase in the rate of all reactions including chain transfer to monomer. Therefore, a preferred catalyst will be one reactive enough to promote reinitiation from the active halide chain ends at lower temperatures or to successfully compete with chain transfer to monomer at high temperatures.

Optionally, appropriate solvents such as organic fluids or mixtures of organic fluids may be utilized. Naturally, solvents which do not interfere with the reaction are used and suitable solvents include organic solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, xylene, diphenylether, 1 ,2-dichloro ethane, dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, dimethylsulfoxide, (DMSO) ketones or esters or any of the other solvents and plasticisers for PVC and their copolymers known in the literature and to those skilled in the art. The amount of solvent used depends on the desired solubility of the system, on the temperature and the desired pressure in the reaction vessel and can be easily determined by one skilled in the art. The amount of solvent generally ranges from about 25 to about 1000, desirably from about 50 to about 500, and preferably from about 75 to about 400 parts per 100 parts of halide containing monomer, such as vinyl chloride.

Alternatively, it has been found that the living free radical polymerization of vinyl chloride can be carried out in the absence of solvent. In such situations, the polymerization is generally carried out in bulk and the other reaction conditions set forth hereinabove are generally suitable.

Alternatively, it has also been found that the living radical polymerization of vinyl chloride can be carried out in water and in water/organic solvent mixtures using the aforementioned solvents as well as other solvents. The presence of an emulsifier such as sodium dodecylsulfate (NaDDS) is optional. The aforementioned conditions still apply. In addition, it was also found that the Cu(0)/TREN, Cu₂Y/TREN (Y = O, S, Se, Te), and CuX/TREN (X = Cl, Br, I, SPh, SBu, C = CPh) catalyst and ligand systems or mixtures thereof can successfully catalyze VC polymerization initiated from iodo, bromo or chloro containing initiators to complete conversion at room temperature. The amount of the optional emulsifier depends of the desired particle size, nature of the emulsifier, and the water to monomer ratio and can be easily selected by one skilled in the art.

Depending on the desired properties of the homopolymer or copolymer, the polymerizations can be either batch, semi-batch or continuous. Mechanical agitation is desirable, but not necessary. Normal polymerization time depends on the temperature and the monomer to initiator to catalyst to ligand ratios and is from 0.5 to about 24 hours. Subsequent to the formation of the polymer composition, solvent and excess monomer are removed, for example by evaporation, precipitation of the polymer, and the like.

In a second embodiment, in the aqueous room temperature non- metal-catalyzed polymerization of halogen containing monomers, appropriate initiators include halides of the formula RX, where R, having 1 - 1 , 000 carbon atoms, contains an activated electron withdrawing group such as a halogen, polyhalo, or perfluoroalkyl, and X - halide (where X^' is a good living group and X = Cl, Br, I). The halide initiator can accept one electron and then release X^" forming an initiating radical R\

RX + RX R +

Such electron-accepting radical precursors include, but are not limited to, various activated mono, di, tri and polyfunctional activated halides. These include α,α-dihaloalkanes, α,α,α-trihaloalkanes, perhaloalkanes, perfluoroalkyl halides, polyfluoroalkyl halides, α-haloesters, α- halonitriles, α-haloketones, benzyl halides, sulfonyl halides, imidyl halides, or combinations thereof. Additionally, any compounds having labile carbon-halide, nitrogen-halide, phosphorus-halide, silicon- halide bonds, which possess enough electron affinity to accept one electron and then release halide-anion forming radicals, are suitable for use as initiators in the present invention, and can include, for example, benzyl iodide, N-iodosuccinimide, diphenylposphinic iodide, triphenylsilyl iodide, and the like. Generally, preferred initiators are one electron accepting radical precursors including chlorine and bromine, with iodine initiators being desirable. Haloforms, tetrahalocarbons, methylene iodide, 1 -chloro-1 - iodo-ethane, as well as PVC's obtained from them, act as active initiators in conjunction both with Na₂S₂0₄, H₂NC( = NH)S0₂H, which give the highest efficiency, and also HOCH₂S0₂Na, HOC^SOsNa, Na₂S0₃, Na₂S₂0_E, Na₂S₂0₃, CH3S0₂Na, CeHsSO∑Na, p-CH3CeH₄SO₂Na, (Me₂N)₂C = C(NMe₂)₂. It should be noted that the system sodium persulfate - sodium formate (Na₂S₂0s - HCOONa, which form C0₂ ^"- radical anion) is active in radical (not living) polymerization of vinyl chloride in conjunction with only non-iodine containing halocarbon initiators - CHCIs, CHBrs (Figures 9, 10), CCU, CBr₄. Whereas, in conjunction with CHta, the persulfate-formate system is not effective at all due to evolution of l₂ which terminates the polymerization. Preferred initiators include iodoform, 1 -chloro-1 -iodoetane, and 1 - iodoperfluoroalkane.

The amounts of the initiators utilized depend on the desired molecular weight of the halide containing polymer and are generally from about 5000 to about 1 , desirably from about 1000 to about 10, and preferably from about 500 to about 50 of halide containing monomer per mole of initiating group. Generally the number average molecular weight of the halide containing polymer will be from about 500 to about 60,000, desirably from about 1 ,000 to about 40,000, and preferably from about 2,000 to about 20,000.

The vinyl halide monomers which are polymerized or copolymerized according to this invention are vinyl chloride and its structurally related derivatives, including vinylidene chloride and 2- chloropropene and monomers known to copolymerize via a radical mechanism with vinyl chloride, including one or more of acrylates, vinylidene halides, methacrylates, acrylonitrile, methacrylonitrile, vinyl halides, 2-haloalkenes, styrenes, acrylamide, methacrylamide, vinyl ketones, N-vinylpyrrolidinone, vinyl acetate, maleic acid esters, or combinations thereof. The preferred carbon atom range of each group of monomers is from 2 to 20. The copolymer can have a comonomer content from 1 % up to 99%, depending on the reactivity ratios of the comonomers used.

An important component of the second embodiment is the use of a non-metallic single electron transfer species to catalyze the initiation reaction and continue the growth of the polymer chain. Typical of such catalysts are, for example, low valent sulfur salts containing S0₂ group and polydialkylamino-substituted unsaturated organic compounds. Examples of such catalysts include Na₂S₂0₄, H₂NC( = NH)S0₂H, H0CH₂S0₂Na, HOCH₂SO₃Na, Na₂S0₃, Na₂S₂0₅, Na₂S₂0s, CHsSOuNa, CeH5S0₂Na, p-CH3C₆H₄S0₂Na,

(Me₂N)₂C = C(NMe₂)₂, and the like. The preferred catalyst will be dependent upon the initiator utilized and on the reaction media (such as solvent or water) and temperature. Preferred catalysts include sodium dithionite (Na₂S₂0 ) and formamidinesulfinic acid (H₂NC( = NH)S0₂H).

The amount of catalyst is dependent upon the desired reaction rate. Generally, the amount of catalyst will be from about 0.01 to about 4, desirably from about 0.05 to about 2, and preferably from about 0.1 to about 1 mole per mole of initiator.

A buffer compound can optionally be included in the polymerization process in order to avoid acidic decomposition of sulfur containing catalysts. The buffer used will depend specifically and uniquely on the type of catalyst, the temperature of the reaction and on the reaction media such as solvent or water. Typical buffers can include alkaline salts of inorganic and organic acids, which water solutions keep pH 8 - 10, such as NaHCOs, Na₂HP0₄, NaH₂P0₄, CHsCOONa or the potassium or ammonium salts thereof, including KHCOs, K₂HP0₄, KH₂P0₄, CHsCOOK, NH4HCO3, (NH₄)₂HP0₄, NH₄H₄P0₄, CH₃C00NH₄, and the like.

When the optional buffer is present, the mixture will usually contain from about 0.1 to about 5 moles of buffer per mole of catalyst, desirably from about 0.5 to about 3 moles of buffer per mole of catalyst, and preferably from about 1 to about 1 .2 moles of buffer per mole of catalyst.

The presence of an electron shuttle is also optional. The shuttle allows for acceleration of the process of radical initiation and activation of dormant species by using compounds which, in reduced form are more soluble in organic phase than in water, and which in oxidized form are more soluble in water than in organic solvent. In a reduced state in the aqueous phase (having gained an electron), the compound moves into the organic phase and donates an electron to the halogen-containing initiator or dormant species. The compound then returns to the aqueous phase carrying the halide anion and leaving a radical in the organic phase. Such compounds can include 1 , 1 '-dialkyl-4,4'-bipyridinium dihalides called alkyl viologens. Examples of such shuttles include, but are not limited to, 1 ,1 '-dimethyl-4,4'- bipyridinium dichloride, methyl viologen (MV²⁺), 1 ,1 '-di-n-octyl-4,4'- bipyridinium dibromide, octyl viologen (OV²⁺), and the like. When the shuttle is present, the mixture will usually contain from about 0.00001 to about 1 moles of shuttle per mole of catalyst, desirably from about 0.0001 to about 0.01 moles of shuttle per mole of catalyst, and preferably from about 0.001 to about 0.005 moles of shuttle per mole of catalyst.

Additionally, various additives may optionally be utilized in the polymerization. Depending on their structure, these additives may affect the molecular weight, molecular weight distribution of the resulting polymer, catalyst stability and/or rate of polymerization. Such additives can include sodium iodide, ammonium iodide, tetrabutyl ammonium iodide, and sodium chloride. These can be added in similar amounts as the initiators.

The non-metallically catalyzed polymerization reactions described herein are normally carried out in the presence of catalyst and initiator in a closed vessel in an inert atmosphere such as nitrogen or argon, under autogenously or artificially induced pressure. The optimal temperature of the polymerization is around room temperature, namely 25°C ± 5 °C. A higher temperature can lead to fast reduction of active chain ends and a lower one is simply inconvenient due to necessity to use special cooling equipment. This can lead to higher viscosity, heterogeneity and reduced solubility of reaction components that make results less reproducible.

Appropriate solvents such as water or a mixture of water and organic solvent may be utilized. Solvents play an important role in single electron transfer. It was found that there is no reaction in the absence of water when salts are used. The higher the solvent polarity is, the more efficient is the polymerization. By this means, polar water-soluble organic solvents and good PVC solvents such as tetrahydrofuran (THF), dimethylformamide (DMF), dimethylsulfoxide (DMSO), cyclohexanone, chlorobenzene, dichlorobenzene, trichlorobenzene, xylene, diphenylether, 1 ,2-dichloroethane, dioxane, acetone, diethyloxalate, ethylhexyphtalate, methanol, ethanol, butanol, or combinations thereof, or any other solvent in the literature known to those skilled in the art are appropriate media for the polymerization. The amount of the solvent generally ranges from 1 to 10 parts per volume of halide containing monomer and preferably is from about 2 to about 4 parts per volume (ppv).

The presence of a surfactant is optional. Examples of the surfactants include, but are not limited to, sodium dodecylsulfate (NaDDS), hydroxypropyl methylcellulose (Methocel^® F50), 72.5% hydrolyzed polyvinyl acetate (Alcotex^® 72.5), polyoxyethylene(I O) oleyl ether (Brij^® 97), and polyoxyethylene(20) oleyl ether (Brij^® 98). The amount of the optional surfactant depends on the desired particle size, nature of the surfactant and the water to monomer ratio. This can be easily selected by one skilled in the art. The amount of surfactant generally ranges from about 0.1 to about 50000 parts per million (ppm) w/w, desirably from about 1 to about 10000 ppm w/w, and preferably from about 10 to about 5000 parts per million w/w relative to halide containing monomer.

Depending on desired properties of the homopolymer or copolymer, the polymerization can be batch or semi batch, or continuous. Mechanical agitation is desirable to obtain reproducible results, but not necessary. Normal polymerization time depends on the monomer - initiator ratio and desirable polymer properties and can be from about 1 h to about 70 h. Subsequent to the formation of the polymer composition, solvent and excess monomer is removed, for example by evaporation of the vinyl chloride and the addition of methanol to precipitate the polymer.

An advantage of the living radical polymerization process described herein is that it will produce a halogen-containing polymer, such as PVC, with controlled molecular weight, such that the molecular weight increases with the conversion of the monomer. Additionally, the living radical polymerization process will provide PVC with narrow molecular weight distribution and with the well defined chain ends, i.e. telechelics and macromonomers. Such molecular weight distribution, i.e. Mw/Mn, can be from < 2.00, ≤ 1.90, or < 1 .80 down to < 1 .70, < 1 .60, or even < 1 .50. A molecular weight distribution of from about < 1 .70 to about < 1 .50 is preferred and less than 1 .50 is most preferred. Since the structural defects in PVC are responsible for its low thermal stability, PVC obtained by living radical polymerization will be more stable than conventional PVC, thereby expanding the range of technological applications of PVC.

The poly(vinyl chloride) compositions described herein can be useful for many applications including plastic materials (sheeting, films, molded parts, etc.), viscosity/flow modifiers, additives for flame retardant compositions, and compatibilizers.

The following examples show ways in which the invention can be practiced, as well as comparative examples. However, the examples do not limit the invention. Table 1. Polymerization of Vinyl Chloride Initiated from Various Halides and Catalyzed by Fe(0).

Exp Initiator Catalyst/Ligand [VC]:[I]:[C]:[L] ^al Time Conv. Mn Mw/Mn Temp Solvent h % °C

1 Br-(CH₃)2C(COOEt) Fe(0)/Phen 65:1:0.6:1 19 26 10,000 1.66 90 oDCB

2 Br-(CH₃)₂C(COOEt) Fe(0)/Phen 130:1:1.2:2 22 19 7,000 1.75 90 THF

3 Br-(CH₃)2C(COOEt) Fe(0)/Phen 130:1:1.2:2.4 22 16 7,200 1.85 90 DMF

4 Br-(CH₃)2C(COOEt) Fe(0)/Phen 130:1:1.2:2 40 15 19,100 1.65 60 oDCB

5 Br-(CH₃)₂C(COOEt) Fe(0)/P en 130:1:1.2:2.4 22 30 10,200 1.73 90 oDCB

6 Br-(CH₃)2C(COOEt) Fe(0)/Phen 130:1:1.2:2.4 22 33 8,300 1.85 130 oDCB

7 Br-(CH₃)2C(COOEt) Fe(0)/Phen 120:1:1.2:2.4: 20 42 9,000 1.75 90 oDCB

Br-(CH₃J2C{COOEt) Fe(0)/Phen/AI'^'Bu3 130:1:1.2:2:1.2 22 10 12,900 1.59 90 oDCB

9 CI-(CH₃)C(COOMe)- Fe(0)/Phen 450:1:4.5:3.5 22 35 8,300 1.73 90 oDCB

10 Br-C(CHs)2-CO-0-Ph- Fe(0)/Phen 130:1:2:4 96 36 8,400 1.75 90 oDCB -Ph-OCO-C(CH₃)₂-Br

11 Br-CH(P )CH₃ Fe(0)/Phen 130:1:1.2:2 19 27 12,500 1.75 90 oDCB

12 Br-CH2-P -CH₂-Br Fe(0)/Phen 130:1:1.2:2.4 22 10 13,300 1.5 90 oDCB

13 Br-CH₂-Ph-CH2-Br Fe(0)/Phen 130:1:2:4 96 5 2,600 1.96 90 oDCB

14 CI-CH2-Ph-CH₂-CI Fe(0)/Phen 130:1:2:4 96 5 8,300 1.65 90 oDCB

15 l-CH₂-Ph-CH2-l Fe(0)/P en 130:1:2:4 23 10 4,300 1.98 130 oDCB

16 NCS-CH2-Ph-CH₂-SCN Fe(0)/Phen 130:1:2:4 48 8 4.800 1.90 90 oDCB

17 CI-(CN)CHCH₃ Fe(0)/Phen 130:1:1.2:2.4 19 10 9,400 1.61 90 oDCB

18 CI-(CN)CHCH₃ Fe(C0)5 130:1:1.2 18 4 14,300 1.65 90 oDCB

19 Cl-S0₂-Ph-F Fe(0)/Phen 130:1:1.2:2.4 18 22 7,600 1.82 90 oDCB a)Molar ratio of VC to initiator to catalyst to ligand

Table 2. Polymerization of Vinyl Chloride initiated from Various Halides and Cε italyzed by TiCp₂CI₂.

Exp Initiator Catalyst/Additive [VC]:[I]:[C]:[A] ^al Time Conv Mn w/ n Temp Solvent h % °C

20 - TiCp2Cl2 130:0:1 20 3 12,000 1.67 70 oDCB

21 Br-fCHs C-COOEt TiCp2Cl2 130:1:1.2 22 10 15,000 1.78 90 oDCB

22 Br-(CH3)₂C-COOEt TiCp2Cl2 130:1:1.2 20 7 21,400 1.68 60 oDCB

23 Br-(CH3)₂C-COOEt TiCpaCk/AI'Bua 130:1:1.2:3.6 17 60 3,800 2.10 90 oDCB

24 Br-fCHshC-COOEt TiCp2Cl2/Zn/bpy 130:1:1.2:1.8:0 22 22 14,800 1.95 90 oDCB

.7

25 Br-(CH₃)₂C-COOEt Ti(OBu)4/Al'Bu3 130:1:1.2:3.6 17 87 5,300 1.80 90 oDCB

26 Br-C(CH₃)2-CO-0-Ph- TiCp2Cb 520:1:2 20 5 3,100 2.05 130 oDCB Ph-OCO-C(CH₃)₂-Br

27 Br-C(CH₃)2-OCO-Ph-C(CH₃)- TiCp2C 520:1:2 20 7 4,400 1.81 130 oDCB

28 Br-CH₂-Ph-CH2-Br TiCp2Cl2 520:1:2 20 5 3,600 1.86 130 oDCB

29 CI-CH₂-Ph-CH2-CI TiCp₂Cl2 520:1:2 20 28 4,900 1.81 130 oDCB

30 CI-CH2-Ph-CH2-CI TiCp2Cl2 520:1:2 96 38 10,600 1.80 90 oDCB

31 NCS-CH₂-Ph-CH2-SCN TiCp2Cl2 260:1:3.5 22 5 4,000 2.05 130 oDCB

32 CI-CH(CN)CH₃ TiCp∑Ch 130:1:1.2 19 22 16,000 1.72 90 oDCB

33 Br-N(CO-CH₂-CH_rCO) TiCp2Cl2 130:1:1.2 19 4 19,000 1.75 90 oDCB

34 CI₃(-NCO-)₃ TiCp2Cl2 390:1:2.1 20 5 8,200 1.80 90 oDCB

35 (CI-Sθ2-P )3C-CH₃ TiCp∑C 400:1:9 22 7 4,000 2.05 110 oDCB

36 Cl-S0₂-Ph-F TiCp2Cl2 130:1:1.2 19 22 12,000 1.65 90 oDCB a]

Molar ratio of VC to initiator to catalyst to additive

Table 3. Polymerization of Vinyl Chloride Initiated from Various Halides and Catalyzed by Cu(l).

Exp Initiator Catalyst/Ligand [VC]:[ιI:[C]:[L]^a> Time Mn IWw/IW Conv Temp Solvent

37 Br-C(CH₃)₂-CO-0-Ph- CuBr/Mee-TREN 260:1:4:8 20 2,500 1.45 8 130 oDCB

38 Br-C(CH3)₂-CO-0-Ph- CuBr/Mee-TREN 260:1:4:4 20 750 1.80 2 90 oDCB

39 CI-(CN)CHCH₃ CuC^C-Ph/bpy 100:1:1.5:3 19 1,300 3.60 15 90 DMF

40 CI-{CN)CHCH₃ CuSPh/bpy 140:1:0.7:1.2 19 2,800 3.30 13 60 DMF

41 l-CH(CI)-CH3 CuBr/Mee-TREN 260:1:2:4 44 3,200 1.30 5 90 oDCB

42 l-CH(CI)-CH₃ CuBr/Mee-TREN 520:1:4:4 20 4,100 1.27 3 130 oDCB

43 l-CH(CI)-CH₃ CuBr/Mee-TREN 60:1:1:1 20 2,000 1.40 3 90 oDCB

44 l-CH(CI)-CH₃ Cul/Mee-TREN 130:1:1:1 20 1,700 1.21 2 90 oDCB

45 l-CH₂-Ph-CH2-l CuBr/Mee-TREN 520:1:8:8 20 4,400 1.50 4 130 oDCB

46 NCS-CH2-PI1-CH2-SCN Cu2Te/bpy 260:1:4:8 22 5,100 2.23 8 130 oDCB

47 NCS-CH2-Ph-CH₂-SCN CuBr/Mee-TREN 520:1:4:4 20 1,000 1.55 2 130 oDCB

Molar ratio of VC to initiator to catalyst to ligand.

Table 4. Polymerization of Vinyl Chloride Initiated from Various Halides and Catalyzed by Cu (0).

Exp Initiator Catalyst/Ligand [VC]:[I]:[C]:[L] ^al Time, Conv, Mn Mw/M Temp Solvent h % °C

48 CI-CH2-C(CH2-CI)=CH2 Cu(0)/bpy 200:1:4:8 20 31 7,700 1.85 130 oDCB

49 CI-CH2-CH = C(CH₃)2 Cu(0)/bpy 100:1:2:4 20 20 8,300 1.62 130 oDCB

50 CI-CH2-CH=CH2 Cu(0)/bpy 100:1:2:4 20 27 6,100 1.83 130 oDCB

51 CI-CH(CN)CH₃ Cu{0)/bpy 130:1:1.2:1.2 19 20 6.900 1.85 90 DMF

52 CI-CH(CN)CHs Cu(0)/bpy 130:1:1.2:2.4 19 12 7,300 1.93 130 oDCB

53 CI-CH2-CI Cu(0)/bpy 100:1:2:4 20 5 50,000 2.75 130 oDCB

54 CI-CH2-Ph-CH₂-CI Cu(0)/bpy 260:1:4:8 21 34 5,600 1.62 130 oDCB

55 CI-CH2-PI1-CH2-CI Cu(0)/bpy 1000:1:8:16 20 18 22,400 1.53 130 oDCB

56 CI-CH2-Ph-CH₂-CI Cu(0)/bpy 60:1:4:4 20 95 gel - 130 oDCB

57 Br-(CH₃)2C-C0Br Cu(0)/bpy 130:1:4:8 22 12 17,000 1.90 90 oDCB

58 Br-(CHs)2C-COOEt Cu(0)/bpy 130:1:1.2:1.8 22 20 8,100 1.85 90 oDCB

59 Br-(CH₃)₂C-COOEt CufOl/bpy/Al'Bus 130:1:1.2:1.8:1 22 77 6,400 1.85 90 oDCB

.2

60 (Br-CH2)4Ph Cu(0)/bpy 125:1:8:16 20 7 23,700 1.58 130 oDCB

61 Br-C(CHs)2-COO-Ph-C(CH3)2- Cu(0)/bpy 260:1:4:8 17 30 6,300 1.45 130 oDCB Ph-OCO-C(CH₃)₂-Br

62 Br-C(CH₃)2-COO-Ph-C(CH₃)2- Cu(0)/bpy 260:1:4:8 65 42 11,100 1.72 90 oDCB Ph-OCO-C(CH₃)₂-Br

63 Br-C(CH₃)2-COO-Ph-C(CH₃)2- Cu(0)/bpy/Nal 260:1:3:4.5:3 20 20 4,200 1.50 130 oDCB

64 Br-C(CHs)2-CO-0-Ph- Cu(0)/PMDETA 260:1:4:8 20 35 gel " 90 oDCB

65 Br-CfCH -CO-O-Ph- Cu(0)/bpy 260:1:4:8 22 30 5,700 1.48 130 oDCB Ph-OCO-C(CH₃)₂-Br

66 Br-C(CH3)2-OCO-Ph-C(CHs)- Cu(0)/bpy 390:1:6:12 18 14 6,800 1.98 130 oDCB [(Ph-OCO-C(CH₃)2-Br]2

67 Br-CH(CI)-CH3 Cu(0)/bpy 100:1:2:4 20 40 6,000 2.30 130 oDCB

68 Br-CH(P )CH₃ Cu(0)/bpy 130:1:2.2:3 66 26 6,000 1.75 130 oDCB

69

70

71

72

73 l-C(CH₃)2-CO-0-Ph-C(CH₃)2- Cu(0)/bpy 260:1:4:8 21 28 7,000 1.60 90 oDCB

74

75

76 l-CH₂-CH = CH2 Cu(0)/bpy 130:1:1.2:2.2 20 13.5 6,500 1.70 90 oDCB

77 l-CH2-CH = CH₂ Cu(0)/bpy 130:1:5:2.5 22 27 13,100 1.93 90 oDCB

78 l-CH₂-CH = CH2 Cu(0)/bpy 260:1:2:4 24 22 6,800 1.72 130 oDCB

79

Cu(0)/bpy 260:1:2:2 20 12 3,400 1.84 130 oDCB

80 CHI₃ Cu(0)/bpy 50:1:1.5:3 20 8 3,300 1.25 130 oDCB

81 CHIs Cu(0)/bpy 50:1:3:6 20 40 3,700 1.65 130 oDCB

82 CHIs Cu(0)/bpy 150:1:3:6 20 19 4,500 1.35 130 oDCB

83 CHIs Cu(0)/bpy 150:1:1.5:3 20 3 760 1.38 130 oDCB

84 CHIs Cu(0)/bpy 150:1:6:12 20 33 6,100 1.65 130 oDCB

85 CHIs Cu(0)/bpy 1500:1:6:12 20 7 17,400 1.40 130 oDCB

86 CHIs Cu(0)/bpy 1500:1:12:24 20 11 30,000 1.63 130 oDCB

87 CHIs Cu(0)/bpy 1500:1:12:24 20 1 11 00 1.55 90 oDCB

88 CHIs Cu(0)/bpy 3100:1:12:24 20 8 45,000 1.59 130 oDCB

89 CHIs Cu(0)/TREN 150:1:0.75:0.7 20 10 5,000 1.58 130 oDCB

5

90 Ck Cu(0)/bpy 150:1:4:8 20 2 2,500 1.45 130 oDCB

91 Cl4 Cu(0)/bpy 1000:1:8:16 20 7 17,400 1.52 130 oDCB

92 l-CH(CI)-CH₃ Cu(0)/bpy 130 1:2:4 67 28 3,500 1.75 130 oDCB

93 l-CH(CI)-CH₃ Cu(0)/bpy 130 1:2:4 21 42 3,900 1.65 90 oDCB

94 l-CH(CI)-CH₃ Cu(0)/bpy 130 1:2:4 44 36 8,400 1.55 60 oDCB

95 l-CH(CI)-CH₃ Cu(0)/bpy 520 1:2:4 44 13 7,700 1.70 90 oDCB

96 l-CH(CI)-CHs Cu(0)/TREN 520 1:1:1 20 28 7,900 1.65 130 oDCB

97 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 15 5,200 1.78 60 Bulk

98 I-CH(C1)-CH₃ Cu(0)/bpy 100 1:2:4 20 22 5,600 1.77 60 o-DCB

99 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 26 6,200 1.78 60 o-DCB

100 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 14 6.500 1.69 60 o-DCB

101 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 18 5,400 1.87 90 Bulk

102 l-CH(CI)-CH₃ Cu{0)/bpy 100 1 :2:4 20 45 7,800 1.67 90 o-DCB

103 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 55 7,300 1.79 90 o-DCB

104 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 52 8,300 1.68 90 o-DCB

105 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 39 5,500 1.78 130 o-DCB

106 l-CH(CI)-CH₃ Cu(0)/bpy 100 1:2:4 20 38 6,100 1.77 130 o-DCB

107 l-CH(CI)-CH₃ Cu(0)/bpy 1001 2:4 20 43 7,100 1.65 130 o-DCB

108 l-CH(CI)-CHs Cu(0)/bpy 100 1 2:4 20 39 6,800 1.68 130 o-DCB

109 l-CH(CI)-CH₃ Cu(0)/bpy/NaDDS 100 1 2:4:0.1 20 53 10,600 1.65 90 H2O

110 l-CH(CI)-CHs Cu(0)/bpy/NaDDS 100 1 2:4:0.5 20 47 8,500 1.69 90 H2O

111 l-CH(CI)-CH₃ Cu(0)/bpy/NaDDS 100 1 2:4:1 20 41 7,000 1.75 90 H2O

112 [-CH(CI)-CH₃ Cu(0)/bpy/NaDDS 100 1 2:4:2 20 43 7,500 1.66 90 H2O

113 l-CH(CI)-CH₃ Cu(0)/bpy/NaDDS 100 1 2:4:4 20 45 7,300 1.72 90 H2O

114 l-CH(CI)-CHs Cu(0)/bpy/NaDDS 100 1 2:4:0.5 1 30 4,700 1.67 90 H2O

115 l-CH(CI)-CHs Cu(0)/bpy/NaDDS 100 1 2:4:0.5 2 34 6,200 1.71 90 H2O

116 l-CH(CI)-CH3 Cu(0)/bpy/NaDDS 100 1 2:4:0.5 4 44 7,100 1.76 90 H2O

117 l-CH(CI)-CHs Cu(0)/bpy/NaDDS 100 1 2:4:0.5 8 49 8,500 1.72 90 H2O

118 l-CH₂-Ph-CH2-l Cu(0)/bpy 80:1:4:8 20 35 7,900 1.61 130 oDCB

119 l-CH2-Ph-CH₂-l Cu(0)/bpy 130 1 4 8 20 31 10,300 1.58 130 oDCB

120 l-CH₂-Ph-CH2-l Cu(0)/bpy 260 1 4 8 20 19 8,400 1.55 130 Et2Cθ3

121 l-CH₂-Ph-CH2-l Cu(0)/Mee-TREN 260 1 4 4 20 14 3,000 1.80 130 oDCB

122 l-CH2-Ph-CH₂-l Cu(0)/TREN 520 1 4 4 20 37 Gel - 130 oDCB

123 l-CH₂-Ph-CH2-l Cu(0)/bpy 520 1 4 8 20 5 3,100 2.05 130 DMSO

124 l-CH₂-Ph-CH2-l Cu(0}/bpy 130 1 2 4 22 18 6,100 2.02 130 DMF

125 l-CH2-Ph-CH₂-l Cu(0)/bpy 260 1 4 8 1 1.5 1,100 1.98 130 oDCB

126 l-CH₂-Ph-CH2-l Cu(0)/bpy 260 1 4 8 2 6.6 4,100 1.65 130 oDCB

127 l-CH2-Ph-CH2-l Cu(0)/bpy 260 1 4 8 4 11 7,600 1.48 130 oDCB

128 l-CH2-Ph-CH2-l Cu(0)/bpy 260 1 4 8 7 13.4 8,300 1.46 130 oDCB

129 l-CH2-Ph-CH₂-l Cu(0)/bpy 260 1 4 8 13 17.5 10,400 1.48 130 oDCB

130 l-CH₂-Ph-CH2-l Cu(0)/bpy 520 1 4 8 2 2.2 2,100 2.10 130 oDCB

131 l-CH2-Ph-CH2-l Cu(0)/bpy 520 1 4 8 5 7.5 7,019 1.49 130 oDCB

132 l-CH2-Ph-CH2-l Cu(0)/bpy 520 1 4 8 11 11 11,000 1.45 130 oDCB

133 l-CH₂-Ph-CH2-l Cu(0)/bpy/ArBu3 520 1 4 8:2.6 22 20 12,700 1.59 130 oDCB

134 l-CH2-Ph-CH₂-l Cu(0)/bpy 520 1 8 8 21 20 29,600 1.89 130 oDCB

135 l-CH2-Ph-CH2-l Cu(0)/bpy 520 1 16:8 21 43 gel - 130 oDCB

136 l-CH₂-Ph-CH2-l Cu(0)/bpy/DtBP 1000:1:4:8:8 20 16 14,200 1.49 130 oDCB

137 l-CH2-Ph-CH₂-l Cu(0)/bpy 1000:1:16:32 20 17 16,400 1.63 130 oDCB

138 l-CH2-Ph-CH₂-l Cu(0)/bpy 1000:1:8:16 20 9 15,500 1.59 130 oDCB

137 l-CH₂-Ph-CH2-l Cu(θ)/bpy 260:1:4:8 23 20 21,000 1.60 130 oDCB

139 NCS-CH2-Ph-CH2-SCN Cu(0)/bpy 260:1:4:8 20 26 11,000 3.14 130 oDCB

Molar ratio of VC to initiator to catalyst to ligand.

Table 5 Polymerization of Vinyl Chloride catalyzed by Various Metal Derivatives and Metals in their Zero Oxidation Stat

Exp Initiator Catalyst/Ligand [VC]:[I]:[C]:[L] ^al Time, Mn Conv Mw/Mn Temp Solvent h % °C

140 Br-(CH3)2C-COOEt Al(0)/bpy 130:1:1.3:1.1 17 8,200 5 1.61 90 xylene

141 Br-(CH₃)2C-COOEt Al'Bus 130:1:1.14 19 12,800 30 1.68 90 oDCB

1 2 Br-(CH₃)2C-COOEt Cd(0)/bpy 130:1:1.2:1.1 22 14,000 14 1.65 90 oDCB

143 Br-(CHs)₂C-COOEt Sm(0)/bpy 130:1:1.2:1.4 19 11 ,400 11 1.64 90 dioxane

144 Br-(CH3)₂C-COOEt Zn(0)/bpy 130:1:1.2:1.6 20 14,400 15 1.68 90 oDCB

145 C!-CH(CN)-CHs Cr(CO)e 130:1:1.2 18 18,400 9 1.57 90 oDCB

Molar ratio of VC to initiator to catalyst to ligand.

Table 6 Selected Exampl es of the Room Temperature Polymerization of Vinyl Chloride Catalyzed by Copper Catalysts in Water, Solvents and Mixtures Thereof.

Exp Initiator Catalyst [VC]/[I]/ Mn Mw/ Time Conv. Temp° Solvent

147 CH₃-CH(CI)-I Cu(0)/TREN 100/1 /2/4 13,500 1.60 20 67 20 o-DCB

148 CH₃-CH(CI)-I Cu(0)/TREN 100/1/2/4 5,500 1.61 20 45 20 H2O

149 CH₃-CH(CI)-I Cu(0)/TREN 100/1/2/4 3,700 1.47 20 11 20 THF

150 CH3-CH(Ci)-l Cu(0)/TREN 100/1/2/4 4,700 1.57 16 26 20 DMF

151 CH₃-CH(CI)-I Cu(0)/TREN 100/1/2/2 11,500 1.60 20 75 20 o-DCB

152 CHs-CH(CI)-l Cu(0)/TREN 100/1/1/2 7,000 1.65 20 65 20 o-DCB

153 CHs-CH(CI)-l Cu(0)/TREN/Brij-97 100/1/2/4/0.5 5,500 1.91 20 54 20 H2O

154 CH3-CH(CI)-I Cu(0)/TREN/NaDDS 100/1/2/4/0.5 13,200 1.54 20 95 20 H2O

155 CH₃-CH(CI)-I Cu(0)/TREN/NaDDS 100/1/2/4/0.5 2,600 1.91 1 8 20 H2O

156 CH₃-CH(CI)-I Cu(0)/TREN/NaDDS 100/1/2/4/0.5 4,350 1.65 2 27 20 H2O

157 CHs-CH(CI)-l Cu(0)/TREN/NaDDS 100/1/2/4/0.5 6,440 1.56 4 55 20 H2O

158 CH₃-CH(CI)-I Cu(0)/TREN/NaDDS 100/1/2/4/0.5 8,300 1.47 8 62 20 H2O

159 CH₃-CH(CI)-I Cu(0)/TREN/NaDDS 500/1/2/4/0.5 24,000 1.60 48 51 20 H2O

160 CH₃-CH(CI)-I Cu2θ/TREN/NaDDS 100/1/2/4/0.5 12,500 2.43 20 81 25 H2O

161 CHs-CH(CI)-l Cu∑S/TREN/NaDDS 100/1/2/4/0.5 3,700 1.57 20 40 25 H2O

162 CH₃-CH(CI)-I Cu∑Se/TREN/NaDDS 100/1/2/4/0.5 6,800 1.56 20 84 25 H2O

163 CH₃-CH(CI)-I Cu2Te/Cu(0)/ 100/1/1/1/4/0.5 2.900 2.01 15 35 25 H2O TREN/NaDDS

164 CHs-CH{CI)-l Cu₂Te/TREN/ 100/1/2/4 5,500 1.81 15 44 25 H2O

165 CHs-CH(CI)-l Cu2Te/TREN/Brij97 100/1/2/4/0.5 6,500 1.72 17 88 25 H2O

166 CH3-CH(CI)-I Cu2Te/TREN/Brij98 100/1/2/4/0.5 8,600 1.75 17 98 25 H2O

167 CHs-CH(CI)-l Cu∑Te/TREN/NaDDS 100/1/2/4/2.5 6,700 2.10 17 92 25 H2O

168 CH₃-CH(CI)-I Cu2Te/TREN/NaDDS 100/1/2/4/1 8,100 1.68 17 96 25 H2O

169 CH3-CH(CI)-I Cu₂Te/TREN/NaDDS 100/1/2/4/0.5 8,600 1.58 20 96 25 H2O

170 CHs-CH(CI)-l Cu₂Te/TREN/NaDDS 100/1/2/4/0.5 7,900 2.14 14 93 25 H2O

171 CH₃-CH(CI)-I Cu2Te/TREN/NaDDS 100/1/1/2/0.5 5,900 1.75 17 76 25 H2O

172 CH₃-CH(CI)-I Cu∑Te/TREN/NaDDS 100/1/2/4/0.1 5,500 1.76 17 69 25 H2O

173 CH₃-CH(CI)-I CuBr/TREN/Brij 98 100/1/0.5/1/0.5 4,100 1.88 16 31 25 H2O

174 CHs-CH(CI)-l CuCI/TREN/Brij 98 100/1/1/1.5/0.5 8,500 1.86 48 73 20 H2O

175 CH₃-CH(CI)-I CuCI/TREN/Brij-97 100/1/2/4/0.5 19,700 2.02 20 84 20 H2O

176 CHs-CH(CI)-l CuCI/TREN/NaDDS 100/1/2/4/0.5 15,500 2.20 20 67 20 H2O

177 CHs-CH(CI)-l Cul/TREN/Brij-97 100/1/2/4/0.5 20,800 1.97 20 13 20 H2O 178 CH₃-CH(CI)-I CuSPh/TREN/NaDDS 100/1/2/4 5500 1.80 18 60 25 H2O 179 CHIs Cu(0)/PMDETA/NaDD 100/1/2/4 3500 1.59 21 18 25 H2O

S

180 CHIs Cu(0)/TREN/ 100/1/2/4 8330 5.32 87 70 25 MeOH

181 CHIs Cu(0)/TREN/ 100/1/2/4/0.5 1,000 1.47 13 5 25 H2O

(CHs)₃NCιeH33CI

182 CHIs Cu(0 /TREN/NaDDS 1000/1/100/100/ 2 255,,000000 2 2..2200 16 23 25 H2O

5

183 CHIs Cu(0 /TREN/NaDDS 1000/1/100/100/ 3 366,,000000 3 3..6666 87 65 25 H2O

5

184 CHIs Cu(0 /TREN/NaDDS 800/1/30/30/4 43,000 2.29 66 90 25 H2O 185 CHIs Cu(0 /TREN/NaDDS 800/1/15/15/4 33,500 2.44 66 60 25 H2O 186 CHIs Cu(0 /TREN/NaDDS 200/1/4/8/2 14,900 1.63 20 63 20 H2O 187 CHIs Cu(0 /TREN/NaDDS 100/1/8/8/0.5 10,600 1.57 13 94 25 H2O 188 CHIs Cu(0 /TREN/NaDDS 300/1/6/9/1.5 5,800 1.77 16 19 25 MeOH 189 CHIs Cu(0 /TREN/NaDDS 100/1/4/4/0.5 8,400 1.72 17 88 25 H2O 190 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 1,300 1.22 17 8 25 MeOH 191 CHIs Cu(θ: /TREN/NaDDS 100/1/2/4/0.5 1100 1.55 1 10 25 H2O 192 CHIs cu(o; /TREN/NaDDS 100/1/2/4/0.5 1358 1.58 2 20 25 H2O 193 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 1728 1.58 4 25 25 H2O 194 CHIs cu(o; /TREN/NaDDS 100/1/2/4/0.5 1,970 1.56 7 28 25 H2O 195 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 2,800 1.54 14 39 25 H2O 196 CHIs cu(o: /TREN/NaDDS 100/1/2/4/0.5 5500 1.57 24 69 25 H2O 197 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 8400 1.81 62 99 25 H2O 198 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 7,263 1.79 37 93 25 H2O 199 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 8,100 1.83 50 99 25 H2O 200 CHIs cu(o; /TREN/NaDDS 100/1/2/4/0.5 9,300 1.70 16 31 25 Acetone 201 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 10,500 1.80 15 60 25 EtOAc 202 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 8293 1.80 41 99 25 H2O 203 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.5 7980 1.74 30 94 25 H2O 204 CHIs Cu(0 /TREN/NaDDS 800/1/6/6/0.5 6,900 1.77 13 7 25 H2O 205 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.25 9,650 2.28 68 88 25 1/1 MeOH/H₂0 206 CHIs Cu(0 /TREN/NaDDS 100/1/2/4/0.25 13,000 1.91 68 96 25 I/ITHF/H2O

207 CHIs Cu{0 /TREN/NaDDS 100/1/2/4/0.25 11 ,400 1.57 15 96 25 1/1 THF/H2O 208 CHIs Cu(0 /TREN/NaDDS 100/1/1/2/0.5 2,600 1.37 17 35 25 H2O

209 CHIs Cu(0)/TREN/NaDDS 100/1/0.5/1/0.5 1,700 1.35 17 26 25 H₂0

210 CHIs Cu(0)/TREN/NaDDS 100/1/0.5/1/0.5 5700 1.76 87 87 25 H2O

211 CHIs Cu{0)/TREN/THF 100/1/2/4/0 11,100 1.55 15 98 25 I/ITHF/H2O

212 CHIs Cu2Te/Cu(0)/ 100/1/1/1/4/0.5 5,400 1.45 15 65 25 H2O TREN/NaDDS

213 CHIs Cu2Te/CuBr/TREN/ 100/1/1/1/4/0.25/ 1 111,,220000 1 1..5588 14 99 25 THF/H2O 1/1 Brij98/NaDDS 0.25

214 CHIs Cu∑Te/TREN/NaDDS 100/1/8/8/0.5 8,200 1.75 14 99 25 H2O

215 CHIs Cu₂Te/TREN/NaDDS 100/1/6/6/0.5 2,600 1.53 14 54 25 H2O

216 CHIs Cu₂Te/TREN/NaDDS 100/1/4/4/0.5 8,000 1.78 14 98 25 H2O

217 CHIs Cu2Te/TREN/NaDDS 100/1/2/4/0.5 5,900 1.55 13 80 25 H2O

218 CHIs Cu2Te/TREN/NaDDS 100/1/2/4/0.3 11,600 1.53 14 99 25 THF/H2O 1/2

219 CHIs Cu2Te/TREN/NaDDS 100/1/2/4/0.25 6100 1.59 14 82 25 0-DCB/H2O 1/1

220 CHIs Cu2Te/TREN/NaDDS 100/1/1/2/0.5 3,300 1.38 15 45 25 H2O 221 CHIs Cu2Te/TREN/NaDDS 100/1/1/2/0.5 1192 1.70 2 14 25 H2O 222 CHIs Cu₂Te/TREN/NaDDS 100/1/1/2/0.5 2585 1.57 4 38 25 H2O 223 CHIs Cu2Te/TREN/NaDDS 100/1/1/2/0.5 7883 1.82 24 99 25 H2O 224 CHIs Cu₂Te/TREN/NaDDS 100/1/0.5/1/0.5 5,000 1.45 64 66 25 H2O 225 CHIs Cu₂Te/TREN/NaDDS 100/1/0.1/0.5/0.5 850 1.43 64 17 25 H2O 226 CHIs Cu2Te/TREN/NaDDS 100/1/0.1/0.2/0.5 920 1.42 64 11 25 H2O 227 CHIs Cu2Te/TREN/NaDDS 100/1/0.05/0.1/0. 670 1.30 64 2 25 H2O

228 CFs-(CF2)g-l Cu(0)/TREN/Brij-97 100/1/2/4/0.5 5,900 1.66 20 64 20 H2O

229 CH₂ = CH-CH2-I Cu(0)/bpy 100/1/2/4 12,000 1.88 20 5 20 o-DCB

230 BrC(CH₃)2-COOPh- Cu(0)/TREN/NaDDS 200/1/4/8/1 65,000 1.92 20 61 20 H2O

Ph-OCO-CfCHskBr

231 CHsCtPh-OCO- Cu(0)/TREN/NaDDS 300/1/3/4.5 65,000 1.70 20 18 20 H2O

C(CHs)₂Br]s

232 CI-CH₂-Ph-CH2-CI CuCI/TREN/Brij 97 50/1/2/3/0.5 62,300 1.95 20 56 20 H20

233 l-CH2-Ph-CH₂-l Cu(0)/TREN/NaDDS 260/1/4/8/1.3 22,700 1.55 20 13 20 H2O

234 Ph-CO-O-O-CO-Ph CuCI/TREN/Brij 97 100/1/1.5/1 53,100 1.99 20 62 20 H2O

235 PVC, Mn = 5100, Cu(θ)/TREN/NaDDS 740/1/2/4/0.5 29,800 2.62 20 52 20 H2O

Mw/Mn = 1.6

236 PVC, Cu(0)/TREN/NaDDS 1440/1/10/20 55,700 2.94 20 20 20 H2O

Mn = 22,000,

Mw/Mn = 2.2 a) Molar ratio of VC to initiator to catalyst to ligand to surfactan

Table 7. Room temperature Na₂S₂0₄-mediated LRP of VC initiated with iodoform in H₂0 THF

a) Ratio [VC]/[initiator]/[catalyst]/[electron shuttle]/[buffer]/[surfactant] mol/mol/mol/mol/mol/ppm w/w to monomer Table 8. Room Temperature Na₂S₂0₄-mediated LRP of VC Initiated with lodoform in H₂O/THF in the presence of surfactant Brij® 98.

^a) Ratio [VC]/[initiator]/[catalyst]/[electron shuttle]/[buffer]/[surfactant] mol/mol/mol/mol/mol/ppm w/w to monomer

Table 9. Room Temperature Na₂S₂0 -mediated LRP of VC Initiated with llooddooffoorrmm iinn HH₂₂OO//TT:HF in the presence of electron shuttle OV and surfactant Brij® 98

mol/mol/mol/mol/mol/ppm w/w to monomer

10

15 Table 10. Room Temperature Na₂S₂0₄-mediated LRP of VC Initiated with

Iodoform in H₂0/THF in the presence of electron shuttle MV •2+ and surfactant Brij®98

10 ^a) Ratio [VC]/[initiator]/[catalyst]/[electron shuttle]/[buffer]/[surfactant] mol/mol/mol/mol/mol/ppm w/w to monomer Table 11. Room temperature Na₂S₂0₈- HCOONa-mediated radical polymerization of VC initiated with bromoform in H₂O/THF

Table 12. Room temperature Na₂S₂0₈- HCOONa-mediated radical

10 polymerization of VC initiated with chloroform in H₂O/THF

mol/mol/mol/mol mol/ppm w/w to monomer

15

20 Table 13. Room temperature H₂NC(=NH)SO₂H-mediated LRP of VC initiated with iodoform in H₂0/THF in the presence of electron shuttle OV 2+

10

Table 14. Selected examples of the room temperature non-metallic SET reagents- mediated LRP of VC in H₂0, THF and mixtures thereof

Ratio [VC]/[initiator]/[catalyst]/[electron shuttle]/[buffer]/[surfactant] mol/mol/mol/mol/mol ppm w/w to monomer Table 1 presents selected examples of Fe(0) catalyzed VC polymerization. Examples 1 to 9 describe the initiation performed from α-haloesters. Example 9 describes the synthesis of a block copolymer by initiating from the Cl chain end of PMMA synthesized via living radical polymerization. Examples 10 to 16 describe the VC polymerization initiated from benzyl halides and pseudohalides, while examples 17 and 1 8 exemplify α-cyanoesters and example 19 describes the use of sulfonyl halides as initiators. The polymerization may be performed in o-DCB, THF or DMF. In o-DCB, at constant [VC]:[I]:[C]:[L] ratios, lower temperatures lead to higher molecular weights and narrower Mw/Mn but lower conversions (# 4-6).

Table 2 presents the TiCp₂CI₂ catalyzed polymerization of VC initiated from various halides. By itself, in the absence of added initiator, TiCp∑C catalyzes VC polymerization only to very low conversion. Polymers can be obtained in the presence of α-haloesters (examples 21 to 25), benzy halides and pseudohalides (examples 26 to 31 ), α-cyanoesters (example 32) as well as imidyl halides (examples 33 and 34). The addition of AI'BU3 (examples 23 and 25) significantly increase the conversion. Star polymers can be synthesized in the presence of trifunctional initiators (example 27). Lower temperature affords higher Mn but lower conversion (examples 21 and 22). For Ti based catalysts, bhlorine and bromine containing initiators generate higher conversions than iodine initiators and are therefore preferred.

Table 3 presents the Cu(l) catalyzed polymerization of VC initiated from various halides. In the presence of more activating ligands than bpy, such as Me₆-TREN, CuBr can catalyzed VC polymerization initiated from α-haloesters (examples 37 and 38). More reactive Cu(l) species such as CuC ^C-Ph, CuSPh or Cu₂Te (examples 39, 40 and 46) can catalyze VC polymerization even in the presence of bpy as ligand. For the less reactive copper halides, the presence of more activating polyamine ligands is therefore necessary.

Table 4 presents the Cu(0) catalyzed polymerization of VC initiated from various halides. Initiation from allyl chloride defects is demonstrated using various haloallyl model compounds (examples 48- 50) while the initiation from the repeat unit of PVC is demonstrated with the corresponding 1 ,1 -dichloro (example 53), 1 , 1-chlorobromo (example 67) and 1 , 1 -chloroiodo derivatives (examples 92 to 1 17). Cu(0) is also able to catalyze VC polymerization in the presence of a large variety of chloro, bromo and iodo initiators such as α- cyanohalides (examples 51 and 52), α-haloesters (examples 57-59, 61 -66 and 72-74) and various benzyl halides such as α,α'-dichloro-p- xylene (examples 54-56), α,α'-dibromo-p-xylene (example 70) 1 - bromo-1 -phenylethane (examples 68 and 69) and 1 ,2,4,5- tetrakisbromomethyl benzene (example 60, star polymer), α,α'-diiodo- /7-xylene (examples 1 18 to 137). Other successful initiators include perfloroalkyliodides (example 75), allyl iodide (examples 76 to 79), iodoform (examples 80 to 89) and carbon tetraiodide (examples 90 and 91 ).

The experiments described in examples 125-132 are plotted in Figure 1 and show that the molecular weight increases linearly with conversion while the polydispersity decreases with conversion at 130°C using o-DCB as solvent. A linear (Figure 2) dependence between molecular weight and conversion is observed (examples 1 14- 1 1 7) even at 90°C if VC polymerization is carried out in water in the presence of a surfactant (sodium dodecylsulfate). The results from examples 97 to 108 describe the combined effect of VC concentration (from bulk 14.4 M to solution 4.8 M) and temperature (from 60 °C to 1 30°C) on the molecular weight molecular weight distribution and conversion of the resulting PVC for a reaction time of 20 h and are presented in Figure 3. An optimum conversion is observed for [VC] = 7.2 M while bulk polymerization generates both lower conversion as well as lower molecular weight and broader molecular weight distribution. -

Table 5 presents miscellaneous examples of metal catalyzed VC polymerization. It was observed that α-haloesters catalyze VC polymerization (examples 140-144) in the presence of Al(0)/bpy and AI'Bu3 as well as Cd(0)/bpy, Sm(0)/bpy and Zn(0)/bpy. α- Cyanohalides (example 145) can catalyze VC polymerization in the presence of Cr(CO)6.

Table 6 presents selected examples of the room temperature metal catalyzed VC polymerization in water, organic solvents or mixtures thereof. In the presence of activating ligands such as TREN, Cu(0) and its derivatives are successful in polymerizing VC at room temperature. Particularly suitable initiators include iodine derivatives such as CH3-CH(CI)-I (example 147 to example 1 78), CH (example 179 to example 227), CF₃-(CF₂)9-I (example 228), CH₂ = CH-CH₂-I (example 229) and l-CH₂-Ph-CH₂-l (example 233). A demonstration of the Cu(0)/TREN catalyzed living radical polymerization of VC at room temperature initiated from CH3-CH(CI)-I in water is presented in Figure 4. A linear dependence between molecular weight and conversion is observed up to complete conversion of VC. Initiators that generate high Mn PVC at room temperature are also bromine and chlorine containing initiators such as BrC(CH3)₂-COO-Ph-Ph-OCO-C(CH₃)₂Br (example 230) or CH₃C[Ph-OCO-C(CH3)₂Br]₃ (example 231 in which case a star PVC polymer was obtained) or CI-CH₂-Ph-CH2-CI(example 232). Low Mn PVC synthesized by living radical polymerization (example 235) can be chain-extended with VC in water while commercial PVC (example 236) can be grafted in water with VC under the same conditions. Very suitable catalytic systems include Cu(0)/TREN, Cu₂Te/TREN and combinations thereof. By contrast with the solution experiments performed with CuX (X = Cl, Br, I) at higher temperatures, the CuX/TREIM catalytic systems are active in water even at room temperature (examples 173-177, 232). A conventional initiator such as benzoyl peroxide can be employed as well (example 234). The polymerization can also be carried out at room temperature in various organic solvents such as o-DCB, THF, Acetone, Ethyl Acetate, MeOH etc or mixtures water/organic solvent in which case the presence of the surfactant may be not be necessary.

Table 7 presents selected examples of Na₂S₂θ4-catalyzed LRP of VC initiated with iodoform in H₂0/THF. Examples 1 - 22 with the same water-THF ratio 2/1 are plotted in Figure 1 . The two rate constants are observed. k_Pι represents a liquid-liquid emulsion polymerization when k_p2 represents a solid-liquid suspension one. Such a transfer takes place after about 24 h at about 60% of VC conversion. k_Pι > k_p2 more than 2 times (0.0039 h^"1 and 0.O015 h^"1 respectively). Mn is consistent with Mth as for a living process. Polydispersity drastically decreases in the beginning of the polymerization with increasing of Mth and keeps lower than 1 .5 until the end of the process after 66 h (example 19). VC conversion at this point is a little more than 80 %. Example 22 without buffer shows low conversion. Change of the H₂0/THF ratio to 7/3 (example 23) does not have a significant influence on this reaction.

Table 8 presents room temperature Na₂S₂0₄-catalyzed LRP of VC initiated with iodoform in H₂0/THF in the presence of surfactant Brij^® 98. These experiments were carried out with different H₂0/THF ratios both 2/1 and 7/3. Comparison of the experiments, for example, 47 and 48, which are equal except for H₂0/THF ratios (7/3 and 2/1 resp.) shows a little higher yield (80 vs. 78%) and lower polydispersity (1 .54 vs. 1 .55) for the former one after 66 h. Amount of the surfactant varies from 2080 to 16640 ppm w/w relative to VC. Comparing the results of the experiments 26, 54, 55, 56 and 58 for 45 h one can see the increasing of polydispersity with increasing of surfactant amount from 1 .48 to 1 .66, when the VC conversions do not differ essentially each from others. The experiments with H₂0/THF ratio 7/3 and amount of Brij^® 98 2080 ppm w/w relative to VC are plotted in Figure 2. One can also observe two different polymerization rates, namely for emulsion and suspension. In this case k_Pι for the liquid-liquid emulsion polymerization is higher then that rate constant for the non-surfactant process in Figure 1 (0.050 vs. 0.039 h^"1), whereas the two constants k_p2 are similar (0.013 and 0.01 5 h^"1 respectively). The emulsion-suspension transfer also occurs after about 24 h but already at about 70% of VC conversion. The emulsion is kept longer in this case. Mn is in good agreement with Mth. Polydispersity drops fast from 2.4 to less than 1 .5 and is held practically constant up to the end of polymerization.

Table 9 presents results of the room temperature Na₂S₂U4- catalyzed LRP of VC initiated with iodoform in H₂0/THF in the presence of electron shuttle OV²⁺ and surfactant Brij^® 98. All other factors being equal, decreasing of OV²⁺ decreases polydispersity from 1 .49 to 1 .48 (experiments 72 and 67) while the monomer conversions are equal (72%). Increasing of surfactant amount increases monomer conversion but also polydispersity (experiments 71 and 74). Experiments 59 - 70 are plotted in Figure 3. One can see that the rate constant of emulsion polymerizationand k ι is the highest 0.066 h^"1 and the emulsion-suspension transfer occurs at above 70% of monomer conversion after less than 20 h, while the constant of solid-liquid polymerization k _p2 is lower. As in the previous cases Mn is consistent with Mth and polydispersity decreases up to 1 .5 with increasing of Mth up to about 6000 and then is kept close to this value. Monomer conversion is 82% after 66 h.

Table 10 presents results of the room temperature Na₂S₂O4- catalyzed LRP of VC initiated with iodoform in H2O/THF in the presence of electron shuttle MV²⁺ and surfactant Brij^® 98.

Experiments 99, 98 demonstrate a very small increasing of polydispersity from 1 .55 to 1 .56 with increasing of surfactant amount, while monomer conversions are practically equal (70 and 71 % resp.). A marked increase of MV²⁺ (experiment 101 ) lows the conversion (36%) and shows an increase in polydispersity (1 .73) in comparison with lower amounts of methyl viologen (experiments 89,

96, 97, 100). Experiments 81 - 95 are plotted in Figure 4. As one can see MV²⁺ accelerates liquid-liquid emulsion polymerization k_Pι = 0.054 h^"1, while k_p2 is smaller than for the non-electron shuttle involving reactions but bigger than for one of octyl viologen.

Dependence Mn on Mth is similar as for the previous cases as well as polydispersity is. Tables 1 1 and 1 2 along with Figures 5 and 6 present Na₂S₂0s- HCOONa-catalyzed radical polymerization of VC initiated with, respectively, bromoform and chloroform in H₂O/THF. These polymerizations occur only in the presence of no-iodine containing initiators and show a typical free radical dependence M_n on Mth as it can be seen from Figures 9 and 10.

Table 13 presents room temperature H₂NC( = NH)S0₂H- catalyzed LRP of VC initiated with iodoform in H2O/THF in the presence of electron shuttle OV²⁺ . As H₂NC( = NH)S0₂H is an acidic compound twice amount of buffer is used. The results of the experiments are plotted in Figure 7. Both k_Pι and k_p2 are lower than for a dithionite-mediated polymerization. Maximal conversion is below 60%. Mn shows an ideal dependence on Mth. Polydispersity decreases from 1 .9 to 1 .5.

Table 14 presents selected examples of the room temperature non-metallic SET reagents-mediated LRP of VC in H2O, THF and mixtures thereof. The role of the solvent is illustrated by experiments 1 33, 1 34 and 1 54. While in water either in the presence of OV²⁺ or NaDDS reaction occurs there is no dithionite-catalyzed reaction in dry THF. Different halogen containing compounds, other than iodoform, in conjunction with Na₂S₂0₄ can initiate VC polymerization (experiments 143, 144, 145, 146, 149) both in the presence of electron shuttle and surfactant and without them. The C0₂ ^"- radical anion precursor Na₂S₂U8 - HCOONa is active in conjunction with bromo- or chloro- containing initiators (experiments 1 51 , 1 52, 1 62, 1 63). Different S0₂ containing compounds other than Na₂S₂θ4 show activity with iodoform as initiator (experiments 1 52, 1 56, 160, 164, 1 65, 1 66). Some surfactants show activity in experiments 139, 140, 141 , 142, 1 54. Additives such as sodium halides are active (experiments 125 - 132), with the narrowest polydispersity (1 .445) and high yeld obtained in experiment 1 26.

Conversion, % Figure 1. The dependence of the molecular weight (λ, μ) and molecular weight distribution (v, o) on conversion for the metal catalyzed polymerization of vinyl chloride initiated from α,α-diiodo- -xylene at 1 30°C in o-DCB ([VC] = 4.8M). Closed symbols: [VC]:[l]:[Cu(0)]:[bpy] =

260: 1 :4:8; open symbols: [VC]:[l]:[Cu(0)]:[bpy] = 520: 1 :4:8

Conversion, %

Figure 2. The dependence of molecular weight (σ) and molecular weight distribution (v) on conversion for the polymerization of VC initiated from CH3-CHCI-I and catalyzed by

Cu(0)/bpy in water at 90°C in the presence of sodium dodecylsulfate (NaDDS).

[VC]:[CH₃CHCII]:[Cu(0)]:[bpy]:[NaDDS] = 100: 1 :2:4:0.5.

1

[VC], M

Figure 3. The dependence of molecular weight, molecular weight distribution and conversion on temperature and concentration for the polymerization of VC initiated from CH3-CHCI-I and catalyzed by Cu(0)/bpy in bulk and in o- DCB at 60 °C (σ, τ Δ), 90°C (v,θ, + ) and 1 30°C (λ, μ, 5).

[VC]:[CH₃CHCII]:[Cu(0)]:[bpy] = 100: 1 :2:4.

Conversion, %

Figure 4. The dependence of molecular weight (λ) and molecular weight distribution (σ) on conversion for the polymerization of VC initiated from CHs-CHCI-l and catalyzed by Cu(0)/TREN in water at 20°C in the presence of sodium dodecylsulfate (NaDDS).

[VC]:[CH₃CHCII]:[Cu(0)]:[bpy]:[NaDDS] = 100: 1 :2:4:0.5.

Figure 5. Room Temperature Na₂S₂θ4-mediated LRP of VC Initiated with iodoform in H₂0/THF. [VC]/[CHl3]/[Na₂S₂θ4]/[NaHC0₃]

= 200/1 /2/2.2 (mol/mol/mol/mol).

Left, the kinetic plot, conversion (open symbols) and concentration logarithm (closed symbols) on time. Right, the dependence of the number average molecular weight (closed symbols) and molecular weight distribution (open symbols) on theoretical number average molecular weight.

time, h Mthx10^"

Figure 6. Room Temperature Na₂S₂0 -mediated LRP of VC Initiated with iodoform in H₂0/THF in the presence of surfactant Brij^® 98. [VC]/[CHI₃]/[Na₂S₂0₄]/[NaHC0₃]/[Brij^® 98]

200/1 /2/2.2/2080 (mol/mol/mol/mol/mol/ppm w/w to VC).

Figure 7. Room Temperature Na₂S₂0 -mediated LRP of VC Initiated with iodoform in H₂0/THF in the presence of electron shuttle

OV²⁺ and surfactant Brij^® 98.

[VC]/[CH|₃]/[Na₂S₂0₄]/[NaHC0₃]/[OV^{2 +}]/[Brij^® 98]

200/1 /2/2.2/0.001 75/2080 (mol/mol/mol/mol/mol/ppm w/w to VC).

20 40 60 5 10 15 time, h Mt XlO^"3

Figure 8. Room Temperature Na₂S₂0 -mediated LRP of VC Initiated with iodoform in H₂0/THF in the presence of electron shuttle MV²⁺ and surfactant Brij^® 98.

[VC]/[CHl3]/[Na₂S₂0₄]/[NaHC03]/[MV²⁺]/[Brij^® 98]

200/1 /2/2.2/0.001 75/2080 (mol/mol/mol/mol/mol/ppm w/w to VC).

40 80 120 5 10 15 time, h M_thx10^"a

Figure 9. Room Temperature Na₂S₂0s - HCOONa-mediated radical polymerization of VC initiated with bromoform in H₂0/THF. [VC]/[CHBr3]/[Na₂S₂θ8]/[HCOONa]/[NaHC0₃]

200/1 /2/2/2.2 (mol/mol/mol/mol/mol).

40 80 120 5 10 15 time, h thXlO^"3

Figure 10. Room Temperature Na₂S₂Os - HCOONa-mediated radical polymerization of VC initiated with chloroform in H₂0/THF.

[VC]/[CHBr₃]/[Na₂S₂0₈]/[HCOONa]/[NaHC03] 200/1 /2/2/2.2 (mol/mol/mol/mol/mol).

time, h M_thx10^";

Figure 1 1 . Room Temperature H₂NC( = NH)S0₂H-mediated LRP of VC initiated with iodooform in H₂0/THF in the pesence of electron shuttle OV^{2 +}.

[VC]/[CHI₃]/[H₂NC( = NH)S0₂H]/[NaHC0₃]/[OV²⁺] 200/1 /2/4.4/0.0035 (mol/mol/mol/mol/mol) . Left, the kinetic plot, conversion (open symbols) and concentration logarithm (closed symbols) on time. Right, the dependence of the number average molecular weight (closed symbols) and molecular weight distribution (open symbols) on theoretical number average molecular weight.

EXAMPLES OF PREPARATION OF THE CHLORINE CONTAINING POLYMER UTLIZING A METALLIC CATALYST

The polymerizations reported were performed as follows unless otherwise noted: A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing solvent (ortho-dichlorobenzene, 10 mL), initiator catalyst, ligand, optional additive and vinyl chloride (5 mL, 0.072 mol), was degassed by three freeze-vacuum pump-thaw cycles was filled with argon. The reaction mixture was slowly heated to the specific reaction temperature in an oil bath. After the specific reaction time, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried. The conversion was determined gravimetrically and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were determined by gel permeation chromatography using a calibration based on polystyrene standards. GPC analysis of the polymers was performed on a Perkin-Elmer Series 10 high pressure liquid chromatograph equipped with an LC-100 column oven (22°C), a Nelson Analytical 900 Series integrator data station, a Perkin-Elmer 785A UV/Visible Detector (254 nm), a Varian Star 4090 Rl detector and 2 AM gel (10 μm, 50θΛ and 10 μm, 10⁴ Λ) columns. THF (Fisher, HPLC-grade) was used as eluent at a flow rate of 1 mL/min. A number of polymerization reactions were produced in accordance with the above description. Selected examples from the Tables 1 -6 are presented below:

Table 1 , Example 1 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (ortho-dichlorobenzene (o-DCB), 10 mL), initiator (ethyl 2-bromoisobutyrate, 223 mg, 1 .1 2 mmol), catalyst (Fe(0), 40 mg, 0.7 mmol) and ligand (phen 200 mg, 1 .1 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 9 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .1 7 g (26 %) of PVC, Mn = 10,000, Mw/Mn = 1 .66.

Table 1 , Example 9

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (chlorine terminated poly(methylmethacrylate) PMMA-CH₂-C(COOMe)(CH₃)-CI, Mn

6,300, Mw/Mn = 1 .25, 1 g, 0.1 6 mmol), catalyst (Fe(0), 40 mg, 0.7 mmol) and ligand (phen 100 mg, 0.55 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (20 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 3.5 g (35 %) of PVC, Mn = 8,300, Mw/Mn = 1 .73.

Table 1 , Example 18

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1-chloro-1 - cyanoethane, 79 mg, 0.56 mmol), catalyst (Fe(CO>5, 1 33 mg, 0.68 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 18 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.23 g (4 %) of PVC, Mn = 14,300, Mw/Mn = 1 .65.

Table 1 , Example 19

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (4- florobenzenesulfonyl chloride 1 32 mg, 0.56 mmol), catalyst (Fe(0), 40 mg, 0.7 mmol) ) and ligand (phen 200 mg, 1 .1 2 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 18 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 g (22 %) of PVC, Mn = 14,300, Mw/Mn = 1 .82.

Table 2, Example 21

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol) and catalyst (TiCp₂CI₂, 1 67 mg, 0.67 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.47 g (10 %) of PVC, Mn = 14,300, Mw/Mn = 1 .82.

Table 2, Example 23 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (TiCp₂CI₂, 1 67 mg, 0.6 mmol) and additive (Al'Bu3, 2 mmol, 2 mL 1 M in toluene) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 7 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 2.8 g (60 %) of PVC, Mn = 3,800, Mw/Mn = 2.10.

Table 2, Example 24

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (TiCp₂CI₂, 1 67 mg, 0.6 mmol), additive (Zn(0), 65 mg, 1 mmol) and ligand (bpy 100 mg, 0.4 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 7 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 g (22 %) of PVC, Mn = 14,800, Mw/Mn = 1 .95. Table 2, Example 25

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (Ti(OBu)₄, 231 mg, 0.7 mmol), additive (AI'Bu3, 2 mmol, 2 mL 1 M in toluene) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 7 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 4 g (88 %) of PVC, Mn = 14,800 Mw/Mn = 1 .95.

Table 2, Example 29 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-dichloro-p- xylene, 25 mg 0.14 mmol) and catalyst (TiCp₂CI₂, 70 mg, 0.28 mmol), was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .25 g (28 %) of PVC, Mn = 4,900, Mw/Mn = 1 .81 .

Table 2, Example 33

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (N- bromosuccinimide, 100 mg 0.56 mmol) and catalyst (TiCp₂CI₂, 170 mg, 0.68 mmol), was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 9 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.2 g (4 %) of PVC, Mn = 19,000 Mw/Mn = 1 .78.

Table 2, Example 34

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (trichloroisocyanuric acid, 100 mg, 0.56 mmol) and catalyst (TiCp₂CI₂, 1 70 mg, 0.68 mmol), was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 9 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.2 g (4 %) of PVC, Mn = 19,000, Mw/Mn = 1 .80.

Table 2, Example 35

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator ( 1 ,1 , 1 -tris(4- chlorosulfonylphenyDethane, 100 mg, 0.18 mmol) and catalyst (TiCp₂Cb, 400 mg, 1 .6 mmol), was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 10 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.35 g (7 %) of PVC, Mn = 4,000 Mw/Mn = 2.05. Table 3, Example 39

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (DMF, 5 mL), initiator (1 -chloro-1 - cyanoethane, 64 mg, 0.72 mmol) catalyst (copper phenylacetylide, 1 78 mg, 1 .1 mmol) and ligand (bpy, 337 mg, 2.1 6 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 9 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.67 g (15 %) of PVC, Mn = 1 ,300, Mw/Mn = 3.60.

Table 3, Example 40

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (DMF, 5 mL), initiator (1 -chloro-1 - cyanoethane, 51 mg, 0.56 mmol) catalyst (copper thiophenoxide, 69 mg, 0.4 mmol) and ligand (bpy, 337 mg, 2.16 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 60 °C in an oil bath. After 19 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.6 g (1 3 %) of PVC, Mn = 2,800, Mw/Mn = 3.60. Table 3, Example 41

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL), initiator (1 -chloro-1 - iodoethane, 53 mg, 0.28 mmol) catalyst (copper (I) bromide, 61 mg, 0.42 mmol) and ligand (ths[2-(dimethylamino)ethyl]amine (Meβ-TREN), 193 mg, 0.84 mmol) was degassed by three freeze-vacuum pump- thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 44 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.22 g (5 %) of PVC, Mn = 3,200, Mw/Mn = 1 .30.

Table 3, Example 46

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL), initiator (α,α'-dithiocyanato-p- xylene, 61 mg, 0.28 mmol) catalyst (copper (I) telluhde, 285 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 1 .36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.36 g (8 %) of PVC, Mn = 5,100, Mw/Mn = 2.23.

Table 4, Example 48

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (3-chloro-2- chloromethylpropene, 90 mg, 0.72 mmol) catalyst (copper, 1 84 mg, 2.8 mmol) and ligand (bpy, 898 mg, 5.76 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .4 g (31 %) of PVC, Mn = 7,700, Mw/Mn = 1 .85.

Table 4, Example 49

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1 -chloro-methyl-2- butene, 75 mg, 0.72 mmol) catalyst (copper, 92 mg, 1 .4 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.9 g (20 %) of PVC, Mn = 8,300, Mw/Mn = 1 .62.

Table 4, Example 49 A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1 -chloro-methyl-2- butene, 75 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .4 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.9 g (20 %) of PVC, Mn = 8,300, Mw/Mn = 1 .62.

Table 4, Example 50

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (allyl chloride, 55 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .4 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump- thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .2 g (27 %) of PVC, Mn = 6, 100, Mw/Mn = 1 .83.

Table 4, Example 53

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (methylene chloride, 61 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .4 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.25 g (5 %) of PVC, Mn = 50,000, Mw/Mn = 2.75.

Table 4, Example 55 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-dichloro-p- xylene, 1 2 mg, 0.07 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .12 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 21 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.8 g (18 %) of PVC, Mn = 22,400, Mw/Mn = 1 .53.

Table 4, Example 56

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (2.5 mL, 0.036 mol), solvent (o-DCB, 5 mL), initiator (α,α'-dichloro-p- xylene, 105 mg, 0.6 mmol), catalyst (copper, 307 mg, 0.48 mmol) and ligand (bpy, 750 mg, 0.48 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 2.3 g (95 %) of PVC. Table 4, Example 57

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (2-bromo-2- methylpropionyl bromide, 64 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.5 g (1 2 %) of PVC, Mn = 17,000, Mw/Mn = 1 .90.

Table 4, Example 59 A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.6 mmol), catalyst (copper, 40 mg, 0.6 mmol) ligand (bpy, 1 50 mg, 0.96 mmol) and additive (AI'Bu3, 0.6 mmol, 0.6 mL 1 M in toluene) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 3.5 g (77 %) of PVC, Mn = 6,400, Mw/Mn = 1 .85.

Table 4, Example 60

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1 ,2,4,5- tetrakis(bromomethyl)benzene, 1 6 mg, 0.035 mmol), catalyst (copper,

18 mg, 0.28 mmol) and ligand (bpy, 87 mg, 0.56 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.3 g (7 %) of PVC, Mn = 23,700, Mw/Mn = 1 .58.

Table 4, Example 61

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (propanoic acid, 2- bromo-2-methyl-(1 -methylethylidene)-di-4, 1 -phenylene ester 1 50 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.2 mmol) was degassed by three freeze-vacuum pump- thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .7 g (35 %) of PVC, Mn = 6,300, Mw/Mn = 1 .45.

Table 4, Example 65

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (propanoic acid, 2- bromo-2-methyl-4,4'-biphenylene ester 135 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.2 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .35 g (31 %) of PVC, Mn = 5,600, Mw/Mn = 1 .48.

Table 4, Example 67

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1-chloro-1 - bromoethane 103 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.9 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .79 g (40 %) of PVC, Mn = 6,000, Mw/Mn = 2.30.

Table 4, Example 70

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-dibromo-p- xylene 33 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .95 g (43 %) of PVC, Mn = 1 1 ,000, Mw/Mn = 1 .63.

Table 4, Example 72 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (propanoic acid, 2- iodo-2-methyl-4,4'-biphenylene ester 162 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .12 mmol) and ligand (bpy, 350 mg, 2.2 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .75 g (38 %) of PVC, Mn = 6,700, Mw/Mn = 1 .47.

Table 4, Example 74

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1 , 1 , 1 -tris(4-(2- iodo-2-methylpropanoylphenyl))ethane 1 67 mg, 0.19 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.2 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 70 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .7 g (37 %) of PVC, Mn = 8,600, Mw/Mn = 1 .67. Table 4, Example 75

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoperflorodecane 1 80 mg, 0.28 mmol), catalyst (copper, 25 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .2 g (26 %) of PVC, Mn = 5,800, Mw/Mn = 1 .64.

Table 4, Example 78

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (allyl iodide 47 mg, 0.28 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 mmol) was degassed by three freeze-vacuum pump- thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 g (22 %) of PVC, Mn = 6,800, Mw/Mn = 1 .72.

Table 4, Example 80

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoform, CHb, 567 mg, 1 .44 mmol), catalyst (copper, 138 mg, 2.1 1 mmol) and ligand (bpy, 675 mg, 4.3 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.36 g (8 %) of PVC, Mn = 3.300, Mw/Mn = 1 .25.

Table 4, Example 80

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoform, CHb, 190 mg, 0.48 mmol), catalyst (copper, 184 mg, 2.8 mmol) and ligand (bpy, 900 mg, 5.8 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .45 g (33 %) of PVC, Mn = 6.100, Mw/Mn = 1 .65.

Table 4, Example 86 A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoform, CHb, 18.4 mg, 0.05 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.5 g (1 1 %) of PVC, Mn = 30,000, Mw/Mn = 1 .63.

Table 4, Example 88

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoform, CHb, 9.2 mg, 0.02 mmol), catalyst (copper, 1 8 mg, 0.28 mmol) and ligand (bpy, 87 mg, 0.56 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.34 g (8 %) of PVC, Mn = 45,000, Mw/Mn = 1 .59.

Table 4, Example 89

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (iodoform, CHb, 190 mg, 0.48 mmol), catalyst (copper, 23 mg, 0.36 mmol) and ligand (tris(2-aminoethyl)amine (TREN), 52 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.45 g (10 %) of PVC, Mn = 5,000, Mw/Mn = 1 .58.

Table 4, Example 91 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (carbon tetraiodide, CU, 37 mg, 0.07 mmol), catalyst (copper, 37 mg, 0.57 mmol) and ligand (bpy, 1 80 mg, 1 .1 5 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.29 g (7 %) of PVC, Mn = 17,400, Mw/Mn = 1 .52.

Table 4, Example 97

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), initiator (1 -iodo-1 -chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 60 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.66 g (1 5 %) of PVC, Mn = 5,200, Mw/Mn = 1 .78. Table 4, Example 98

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 2.5 mL) initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 60 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 g (22 %) of PVC, Mn = 5,600, Mw/Mn = 1 .77.

Table 4, Example 99 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL) initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 60 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .17 g (26 %) of PVC, Mn = 6,200, Mw/Mn = 1 .78.

Table 4, Example 100

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL) initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 60 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.63 g (14 %) of PVC, Mn = 6,500, Mw/Mn = 1 .69.

Table 4, Example 101

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), initiator (1 -iodo-1 -chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.81 g (18 %) of PVC, Mn = 5,400, Mw/Mn = 1 .87.

Table 4, Example 104

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL) initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.63 g (14 %) of PVC, Mn = 6,500, Mw/Mn = 1 .69.

Table 4, Example 107

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 5 mL) initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol) and ligand (bpy, 450 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .95 g (43 %) of PVC, Mn = 7, 100, Mw/Mn = 1 .65.

Table 4, Example 109 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 137 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)π- SOsNa, (NaDDS, sodium dodecylsulfate), 21 mg, 0.072 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 2.38 g (53 %) of PVC, Mn = 10,600, Mw/Mn = 1 .65.

Table 4, Example 1 10 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)n- Sθ3Na, (NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 2.1 1 g (47 %) of PVC, Mn = 8,500, Mw/Mn = 1 .69.

Table 4, Example 1 1 1

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)π-

Sθ3Na, (NaDDS, sodium dodecylsulfate), 208 mg, 0.72 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .84 g (41 %) of PVC, Mn = 7,000, Mw/Mn = 1 .75. Table 4, Example 1 12

S0₃Na, (NaDDS, sodium dodecylsulfate), 41 6 mg, 1 .44 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .93 g (43 %) of PVC, Mn = 7,500, Mw/Mn = 1 .76.

Table 4, Example 1 12

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)π- Sθ3Na, (NaDDS, sodium dodecylsulfate), 41 6 mg, 1 .44 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .93 g (43 %) of PVC, Mn = 7,500, Mw/Mn = 1 .76. Table 4, Example 1 13

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)n- SO3Na, (NaDDS, sodium dodecylsulfate), 830 mg, 2.88 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 2.02 g (45 %) of PVC, Mn = 7,300, Mw/Mn = 1 .72.

Table 4, Example 1 14

A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)n- Sθ3Na, NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 hour, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .35 g (30 %) of PVC, Mn = 4,700, Mw/Mn = 1 .67. Table 4, Example 1 15

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)n- SOsNa, {NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 2 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .49 g (34 %) of PVC, Mn = 6,200, Mw/Mn = 1 .71 .

Table 4, Example 1 16

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)π- Sθ3Na, {NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 4 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .98 g (44 %) of PVC, Mn = 7, 100, Mw/Mn = 1 .76. Table 4, Example 1 17

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 8 mL), initiator (1 -iodo-l - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (bpy, 450 mg, 2.88 mmol) and surfactant (CH3-(CH₂)π- SO3Na, NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 8 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .98 g (44 %) of PVC, Mn = 8,500, Mw/Mn = 1 .73.

Table 4, Example 1 18

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 25 mg, 0.07 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .57 g (35 %) of PVC, Mn = 7,900, Mw/Mn = 1 .61 .

Table 4, Example 1 19

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 200 mg, 0.56 mmol), catalyst (copper, 143 mg, 2.24 mmol) and ligand (bpy, 700 mg, 4.48 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .48 g (31 %) of PVC, Mn = 10,300, Mw/Mn = 1 .58.

Table 4, Example 120

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (ethylene carbonate, 1 3.2 g, 1 0 mL), initiator (α,α'-diiodo-p-xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 250 mg, 2.21 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.85 g (19 %) of PVC, Mn = 8,400, Mw/Mn = 1 .56.

Table 4, Example 121 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (tris[2-(dimethylamino)ethyl]amine (Mee-TREN) 1 28 mg, 0.56 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.63 g (19 %) of PVC, Mn = 3,000, Mw/Mn = 1 .80.

Table 4, Example 122

A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and

(tris(2-aminoethyl)amine (TREN), 164 mg, 1 .1 2 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield

1 .66 g (37 %) of PVC.

Table 4, Example 123

A 50 mL Ace Glass ^' 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (dimethylsulfoxide, DMSO, 10 mL), initiator (α,α'-diiodo-p-xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 175 mg, 1 .12 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.22 g (5 %) of PVC, Mn = 3, 100, Mw/Mn = 2.05.

Table 4, Example 124 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (dimethylformamide, DMF, 10 mL), initiator (α,α'-diiodo-p-xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.8 g (18 %) of PVC, Mn = 6,100, Mw/Mn = 2.02.

Table 4, Example 125

A 50 L Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1.1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 1 hour, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.07 g (1 .5 %) of PVC, Mn = 1 ,100, Mw/Mn = 1 .98. Table 4, Example 126

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 2 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.3 g (6.6 %) of PVC, Mn = 4, 100, Mw/Mn = 1 .68.

Table 4, Example 127 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 4 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.46 g (1 1 %) of PVC, Mn = 7,600, Mw/Mn = 1 .48.

Table 4, Example 128

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 7 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.61 g (1 3.5 %) of PVC, Mn = 8,300, Mw/Mn = 1 .46.

Table 4, Example 129

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 100 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .1 2 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 13 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.78 g (1 7.5 %) of PVC, Mn = 10,400, Mw/Mn = 1 .48.

Table 4, Example 130

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .12 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 2 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.1 g (2.2 %) of PVC, Mn = 2.100, Mw/Mn = 2.10.

Table 4, Example 131

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 5 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.34 g (7.5 %) of PVC, Mn = 7,000, Mw/Mn = 1 .49.

Table 4, Example 132 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 130 °C in an oil bath. After 1 1 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.49 g (1 1 %) of PVC, Mn = 1 1 ,000, Mw/Mn = 1 .45. Table 4, Example 133

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 36 mg, 0.56 mmol) ligand (bpy, 1 75 mg, 1 .1 2 mmol) and additive (AlBus, 0.26 mL 1 M in tolene, 0.26 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.9 g (20 %) of PVC, Mn = 1 2,700, Mw/Mn = 1 .59.

Table 4, Example 134

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 72 mg, 1 .12 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 21 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.95 g (21 %) of PVC, Mn = 29,600, Mw/Mn = 1 .89. Table 4, Example 135

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 50 mg, 0.14 mmol), catalyst (copper, 144 mg, 2.24 mmol) and ligand (bpy, 1 75 mg, 1 .1 2 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 21 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 1 .9 g (42 %) of PVC.

Table 4, Example 136 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-diiodo-p- xylene, 25 mg, 0.07 mmol), catalyst (copper, 18 mg, 0.28 mmol), ligand (bpy, 88 mg, 0.56 mmol) and additive (2,6-di-^lbutylpyridine, 1 1 5 mg, 0.56 mmol) was degassed by three freeze-vacuum pump- thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 21 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.4 g (9 %) of PVC, Mn = 29,600, Mw/Mn = 1 .89.

Table 4, Example 139

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (α,α'-dithiocyanato- p-xylene, 62 mg, 0.28 mmol), catalyst (copper, 72 mg, 1 .12 mmol) and ligand (bpy, 350 mg, 2.24 mmol) was degassed by three freeze- vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 1 30 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .2 g (26 %) of PVC, Mn = 1 1 ,000, Mw/Mn = 3.14.

Table 5, Example 140

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (xylene, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (aluminium, 20 mg, 0.74 mmol) and ligand (bpy, 100 mg, 0.64 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 7 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.31 g (7 %) of PVC, Mn = 8,200, Mw/Mn = 1 .61 .

Table 5, Example 141 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol) and catalyst (triisobutylaluminium, AI'Bu3, 0.64 mL 1 M in toluene, 0.64 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 1 9 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 1 .35 g (30 %) of PVC, Mn = 8,200, Mw/Mn = 1 .61 .

Table 5, Example 142

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (cadmium, 76 mg, 0.68 mmol) and ligand (bpy, 100 mg, 0.64 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 22 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.6 g (14 %) of PVC, Mn = 14,100, Mw/Mn = 1 .65.

Table 5, Example 143

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (dioxane, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (samarium, 102 mg, 0.68 mmol) and ligand (bpy, 1 50 mg, 0.96 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 19 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.49 g (1 1 %) of PVC, Mn = 1 1 ,400, Mw/Mn = 1 .64.

Table 4, Example 144 A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (ethyl 2- bromoisobutyrate, 1 1 1 mg, 0.56 mmol), catalyst (zinc, 45 mg, 0.69 mmol) and ligand (bpy, 200 mg, 0.96 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.49 g (1 1 %) of PVC, Mn = 1 1 ,400, Mw/Mn = 1 .64.

Table 4, Example 145

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), solvent (o-DCB, 10 mL), initiator (1 -chloro- cyanoethane, 1 1 1 mg, 0.56 mmol) and catalyst (chromium hexacarbonyl Cr(CO)β, 1 50 mg, 0.68 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was slowly heated to 90 °C in an oil bath. After 20 hours, the tube was slowly cooled and excess vinyl chloride was allowed to boil off. Methylene chloride (10 mL) was added and the solution was precipitated into methanol, filtered and dried to yield 0.4 g (9 %) of PVC, Mn = 18,400, Mw/Mn = 1 .57. Table 6, Example 154

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 10 mL), initiator (1 -iodo-1 - chloroethane, 1 37 mg, 0.72 mmol), catalyst (copper, 92 mg, 1 .44 mmol), ligand (TREN, 421 mg, 2.88 mmol) and surfactant (CH3- (CH₂)n-Sθ3Na, NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was stirred at 20 °C in an oil bath. After 20 hours, the tube was slowly opened and excess vinyl chloride was allowed to boil off. THF (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 4.3 g (95 %) of PVC, Mn = 1 3,200, Mw/Mn = 1 .54.

Table 6, Example 218

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve containing vinyl chloride (5 mL, 0.072 mol), deionized water 6 mL and THF 4 mL), initiator (iodoform, 284 mg, 0.72 mmol), catalyst (copper telluride, 367 mg, 1 .44 mmol), ligand (TREN, 421 mg, 2.88 mmol) and surfactant (CH₃- (CH₂)n-S03Na, NaDDS, sodium dodecylsulfate), 63 mg, 0.21 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon. The reaction mixture was stirred at 20 °C in an oil bath. After 14 hours, the tube was slowly opened and excess vinyl chloride was allowed to boil off. THF (10 mL) was added and the mixture was precipitated into methanol, filtered and dried to yield 4.5 g (99 %) of PVC, Mn = 1 1 ,600, Mw/Mn = 1 .53.

Examples of Preparation of the Chlorine containing Polymer utilizing a Non-Metallic Catalyst Materials. Vinyl chloride (VC, 99%) was provided by OxyVinyls. lodoform (99%), and sodium dithionate (85%) were purchased from Lancaster. Chloroform (99%), and bromoform (99%) were purchased from ACROS Organics. Tetrahydrofuran (THF, 99%), methylene chloride (99.5%), and methanol (99.8%) were purchased from Fisher Scientific. Alcotex^® 72.5 was purchased from Harlow Chemical Co., UK. Methocel^® F50 was purchased from the Dow Chemical Company. All other chemicals were purchased from Aldrich and used as received.

Techniques. ¹H- and ¹³C-NMR spectra were recorded on a Bruker DRX500 at 20 °C in CDCb or CD₂CI₂ with tetramethylsilane (TMS) as internal standard. GPC analysis was performed on a Perkin- Elmer Series 10 high-pressure liquid chromatograph equipped with an LC-100 column oven (22 °C), a Nelson Analytical 900 Series integrator data station, a Perkin-Elmer 785A UV-Vis Detector (254 nm), a Varian Star 4090 Rl detector and 2 AM gel (10 μm, 500 A and 10 μm, 10⁴ Λ) columns. Number and weight-average molecular weights were determined against polystyrene standards and were corrected using the Universal Calibration with the following Mark- Houwink parameters for PVC: K = 1 .50 x 10^"2 mL/g, a = 0.77.

The polymerizations reported were performed as follows unless otherwise noted: a 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with 9ml of a previously degassed appropriate mixture of water and THF then filled with argon, closed and frozen using MeOH/dry ice. The initiator (0.22 mmol), catalyst (0.43 mmol), buffer (4.8 mmol), optional additive and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC is determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and backfilling the tube with Argon1 5 times at - 40°C. The valve was closed and the reaction mixture was stirred in a water bath at 25°C _+ 0.5°C, behind a protective shield. After the specified reaction time the tube was slowly opened. The excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration, then dried in a vacuum oven to a constant weight. The conversion was determined gravimetrically. The kinetic plots were constructed from individual experiments, as sampling of the reaction is not possible.

The samples used for spectral analysis were precipitated twice from THF or CH₂Cb solutions in MeOH and dried under vacuum.

A number of polymerization reactions were produced in accordance with the above description. Selected examples from the Tables 1 -8 are presented below.

Table 7, Example 14.

A 50 mL Ace Glass 8648 #15 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with a previously degassed mixture of water (6 mL) and THF (3 mL), then filled with argon, closed and frozen using MeOH/dry ice. Then, the initiator (CHb, 85.5 mg, 0.22 mmol), catalyst (Na₂S₂0₄, 75.6 mg, 0.43 mmol), buffer (NaHCOs, 40.1 mg, 0.48 mmol), and precondensed VC (3 mL, 0.043 mol) were added. The exact amount of VC was determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40 °C. The valve was closed and the reaction mixture was stirred in a water bath at 25 °C _+ 0.5 °C, behind a protective shield. After 33 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 1 .78 g (66.1 %) PVC, Mn

Table 8, Example 44.

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with Brij^® 98 (6,3 mg 5.5 pmol), a previously degassed mixture of water and THF (volume ratio 7/3, 9 mL), then filled with argon, closed and frozen using MeOH/dry ice. The initiator (CHb, 85.5 mg, 0.22 mmol), catalyst (Na₂S₂0₄, 75.6 mg, 0.43 mmol), buffer (NaHCOs, 40.1 mg, 0.48 mmol), and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC is determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40°C. The valve was closed and the reaction mixture was stirred in a water bath at 25°C _+_ 0.5°C behind a protective shield. After 44 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 2.1 6 g (72.18%) PVC, Mn = 9,325; Mw/Mn = 1 .487.

Table 9, Example 73. reduced pressure and filling the tube with Ar 1 5 times at - 40 °C. The valve was closed and the reaction mixture was stirred in a water bath at 25 ^'°C _+ 0.5 °C behind a protective shield. After 24 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mecha'nically, recovered by filtration and dried in a vacuum oven to constant weight to give 2.28 g (75.90%) PVC, M_n

Table 1 1 , Example 106.

A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with a previously degassed mixture of water (6 mL) and THF (3 mL), then filled with argon, closed and frozen using MeOH/dry ice. The initiator (CHBrs, 26.2 mg, 0.22 mmol), catalyst (Na₂S₂0s, 102.4 mg, 0.43 mmol and HCOONa, 29.2 mg, 0.43 mmol), buffer (NaHCOs, 40.1 mg,^' 0.48 mmol), and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC was determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40°C. The valve was closed and the reaction mixture was stirred in a water bath at 25 °C +_ 0.5 °C behind a protective shield. After 1 20 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (150 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 1 .61 g (53.74%) PVC, Mn = 8,593; Mw/Mn = 1 .968.

Table 12, Example 1 10. A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with a previously degassed mixture of water (6 mL) and THF (3 mL), then filled with argon, closed and frozen using MeOH/dry ice. The initiator (CHCb, 26.2 mg, 0.22 mmol), catalyst (Na₂S₂0s, 102.4 mg, 0.43 mmol and HCOONa, 29.2 mg, 0.43 mmol), buffer (NaHCOs, 40.1 mg, 0.48 mmol), and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC was determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40°C. The valve was closed and the reaction mixture was stirred in a water bath at 25 °C _+ 0.5 °C behind a protective shield. After 96 h, the tube was slowly opened, the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 1 .78 g (58.1 5%) PVC, Mn = 8,854; Mw/Mn = 2.1 54.

Table 13, Example 1 16 A 50 m,L Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with a previously degassed mixture of water and THF (volume ratio 7/3, 9 mL), then filled with argon, closed and frozen using MeOH/dry ice. The initiator (CHb, 85.5 mg, 0.22 mmol), catalyst (H₂NC( = NH)S0₂H, 46.9 mg, 0.43 mmol), buffer (NaHCOs, 80.2 mg, 0.95 mmol), optional electron shuttle (OV²⁺, 0.2 mg, 0.39 μmol), and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC was determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40°C. The valve was closed and the reaction mixture was stirred in a water bath at 25 °C _+ 0.5 °C behind a protective shield. After 68 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 1 .65 g (69.87%) PVC, Mn

Table 14, Example 126. A 50 mL Ace Glass 8648 #1 5 Ace-Thred pressure tube equipped with bushing and plunger valve was charged with a previously degassed mixture of water and THF (volume ratio 7/3, 9 mL), then filled with argon, closed and frozen using MeOH/dry ice. The initiator (CHb, 85.5 mg, 0.22 mmol), catalyst (Na₂S₂0 , 75.6 mg, 0.43 mmol), buffer (NaHC0₃, 40.1 mg, 0.48 mmol), optional electron shuttle (OV²⁺, 0.2 mg, 0.39 pmol) and optional additive (Nal, 263 mg, 1 .76 mmol), and precondensed VC (3 mL, 0.043 mol) were then added. The exact amount of VC was determined gravimetrically after the reaction. The tube was closed and degassed through the plunger valve by applying reduced pressure and filling the tube with Ar 1 5 times at - 40 °C. The valve was closed and the reaction mixture was stirred in a water bath at 25 °C _+_ 0.5 °C behind a protective shield. After 66 h, the tube was slowly opened and the excess of VC was allowed to evaporate and the mixture was poured into MeOH (1 50 mL). The polymer was ground mechanically, recovered by filtration and dried in a vacuum oven to constant weight to give 2.10 g (69.87%) PVC, Mn = 8,91 5; Mw/Mn = 1 .445.

Claims

CLAIMSWhat is claimed is:

1 . A polymeric composition comprising: a vinyl halide polymer derived from a radical or a living radical polymerization of vinyl halide monomer in the presence of: an initiator; a metal-free catalyst; and optionally, a buffer, an electron shuttle, a surfactant and a solvent or water.

2. A polymeric composition according to claim 1 , wherein said vinyl halide monomer is one or more of vinyl chloride, vinylidene chloride or 2-chloropropene.

3. A polymeric composition according to claim 2, wherein said initiator is a halogen containing initiator and said initiator contains one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α-trihaloalkane, a perhaloalkane, a perfluoroalkyl halide, a polyfluoroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof.

4. A polymeric composition according to claim 3, wherein said halogen is one or more of chlorine, bromine, or iodine, and said initiator is present in an amount from about 5000 to about 1 moles of halide containing monomer per mole of initiating group.

5. A polymeric composition according to claim 4, wherein said initiator is iodoform, 1 -chloro-1 -iodoetane, or 1 - iodoperfluoroalkane.

6. A polymeric composition according to claim 3, wherein said catalyst is a non-metal reducing, single electron transfer species.

7. A polymeric composition according to claim 5, wherein said catalyst is a S0₂-containing compound, or a polydialkylamino- substituted unsaturated organic compound, and said catalyst contains one or more of Na₂S₂θ4, H₂NC( = NH)S0₂H, HOCH₂S0₂Na, HOCH₂S0₃Na, Na₂S0₃, Na₂S₂0s, Na₂S₂0₃, CHsSO∑Na, CeH5S0₂Na, p- CH3CeH4S0₂Na, (Me₂N)₂C = C(NMe₂)₂, or combinations thereof.

8. A polymeric composition according to claim 6, wherein said catalyst is present in an amount of from about 0.01 to about 4 moles per mole of initiating group in the initiator, and said catalyst is sodium dithionite or formamidinesulfinic acid.

9. A polymeric composition according to claim 1 , including said buffer, wherein said buffer includes one or more of NaHCθ3, Na₂HP0₄, NaH₂P0 , CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CH3COOK, NH₄HC0₃, (NH₄)₂HP0₄, NH₄H₂P0₄, CH3COONH4 or combinations thereof, and said buffer is present in an amount from about 0.1 to about 5 moles of buffer per mole of catalyst.

10. A polymeric composition according to claim 1 , further including a comonomer, wherein said comonomer is a monomer known to copolymerize with vinyl chloride via a radical mechanism and said comonomer is one or more of acrylates, vinylidene halides, methacrylates, acrylonitrile, methacrylonitrile, vinyl halides, 2- haloalkenes, styrenes, acrylamide, methacrylamide, vinyl ketones, N- vinylpyrrolidinone, vinyl acetate, maleic acid esters or combinations thereof, and said comonomer is present in an amount of from about 1 % up to about 99%.

1 1 . A polymeric composition according to claim 10, wherein said comonomer is vinylidene chloride, 2-chloropropene, acrylonitrile, acrylic acid esters or maleic acid esters and said comonomer is present in an amount from about 1 % to about 99%.

12. A polymeric composition according to claim 1 comprising vinyl chloride, an initiator containing one or more of a mono, di, tri or polyfunctional α,α-dihaloalkanes, α,α,α-trihaloalkanes, perhaloalkanes, perfluoroalkyl halides, polyfluoroalkyl halides, α-haloesters, α- halonitriles, α-haloketones, imidyl halides, and a catalyst containing one or more of a S0₂-containing compound or an Na₂S₂0₄, H₂NC( = NH)S0₂H, HOCH₂S0₂Na, HOCH₂S0₃Na, Na₂S0₃, Na₂S₂0_ε, Na₂S₂0₃, CH₃S0₂Na, CeHsSO^a, p-CH3CeH4S0₂Na, one or more of polydialkylamino-substituted unsaturated organic compound or an (Me₂N)₂C = C(NMe₂)₂ or combinations thereof.

13. A polymeric composition according to claim 6, including said electron shuttle, wherein said electron shuttle is a 1 ,1 '-dialkyl- 4,4'-bipyridinium dihalide.

14. A polymeric composition according to claim 1 3, wherein said electron shuttle is on or more of 1 , 1 '-dimethyl-4,4'-bipyridinium dichloride, 1 , 1 '-di-n-octyl-4,4'-bipyridinium dibromide, or combinations thereof, and said electron shuttle is present it an amount from about

0.00001 to about 1 mole of shuttle per mole of catalyst.

1 5. A polymeric composition according to claim 13, including said surfactant, wherein said surfactant is on or more of sodium dodecylsulfate, hydroxypropyl methylcellulose, 72.5% hydrolyzed polyvinyl acetate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, or combinations thereof, and said surfactant is present in an amount from about 10 to about 5000 parts per million w/w relative to halide containing monomer.

16. A polymeric composition according to claim 1 , wherein said initiator contains one or more of a mono, di, tri or polyfunctional α-α-α-trihaloalkane, a perhaloalkane, a perfluoroalkyl halide, a polyfluoroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof; said catalyst is a S0₂-containing compound or a polydialkylamino-substitured unsaturated organic compound; said buffer is on or more of NaHCOs, Na₂HP0₄, NaH₂P0₄, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄₍ CHaCOOK, NH4HCO3, (NH₄)₂HP0₄, NH₄H₂P0₄, CH3COONH₄, or combinations thereof; said electron shuttle is a l,l'-dialkyl-4,4'-bipyrridinium dihalide; and said surfactant is one or more of sodium dodecylsulfate, hydroxypropyl methylcellulose, 72.5% hydrolyzed polyvinyl acetate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, or combinations thereof.

17. A polymeric composition according to claim 4, wherein said halogen containing initiator is part of a polymer chain, including the chain ends of the said polymer.

18. A viscosity modifier, flame retarding agent or a compatibilizing agent, containing the composition of claim 1 .

19. A viscosity modifier, flame retarding agent or a compatibilizing agent, containing the composition of claim 5.

20. A viscosity modifier, flame retarding agent or a compatibilizing agent, containing the composition of claim 7.

21 . A viscosity modifier, flame retarding agent or a compatibilizing agent, containing the composition of claim 13.

22. A viscosity modifier, flame retarding agent or a compatibilizing agent, containing the composition of claim 1 5.

23. A composition according to claim 1 , wherein the molecular weight distribution of said composition is from about < 2.0 down to about < 1 .5.

24. A composition according to claim 23, wherein said molecular weight distribution is from about <1 .5 down to about <1 .1 .

25. A process for the preparation of a chlorine containing polymer comprising the steps of: forming a mixture comprising a vinyl chloride monomer; and optionally, a comonomer, in the presence of: an initiator, a metal-free catalyst; and optionally, a buffer, an electron shuttle, a surfactant; and a solvent or water; and polymerizing said vinyl chloride monomer to form a polymer or copolymer by a radical or a living radical process.

26. A process according to claim 25, wherein said initiator is a halogen containing initiator.

27. A process according to claim 26, wherein said initiator is a halogen containing initiator and said initiator contains one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α-trihaloalkane, a perhaloalkane, a perfloroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof.

28. A process according to claim 27, wherein said halogen is one or more of chlorine, bromine, or iodine.

29. A process according to claim 28, wherein said catalyst is a non-metal reducing, single electron transfer agent.

30. A process according to claim 29, wherein said catalyst is one or more of SO∑-containing compounds, including Na₂S₂0₄, H₂NC( = NH)S0₂H, HOCH₂S0₂Na, HOCH₂S0₃Na, Na₂S0₃, Na₂S₂0₅, Na₂S₂0₃, CH3S0₂Na, C₆H₅S0₂Na, p-CH₃C6H₄S0₂Na, or a polydialkylamino-substituted unsaturated organic compound, including (Me₂N)₂C = C(NMe₂)₂, or combinations thereof.

31 . A process according to claim 30, wherein said catalyst is present in an amount of from about 0.01 to about 4 moles per mole of initiating group in the initiator, and said catalyst is sodium dithionite or formamidinesulfinic acid.

32. A process according to claim 29, wherein said initiator is present in an amount from about 10,000 to about 1 moles of vinyl chloride monomer per one mole of initiator and said vinyl chloride monomer is vinyl chloride.

33. A process according to claim 30, including said buffer, wherein said buffer includes one or more of NaHCOβ, Na₂HP0 ,

NaH₂P0₄, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CHsCOOK, NH₄HC0₃, (NH₄)₂HP0₄, NH₄H₂P0₄, CH3COONH4 or combinations thereof, and said buffer is present in an amount from about 0.1 to about 5 moles of buffer per mole of catalyst.

34. A process according to claim 25, further including said comonomer, wherein said comonomer is an acrylate, a vinylidene halide, a 2-haloalkene, a methacrylate, an acrylonitrile, a methacrylonitrile, a vinyl halide, a styrene, an acrylamide, a methacrylamide, a vinyl ketone, a N-vinylpyrrolidinone, a vinyl acetate, a maleic acid ester or combinations thereof, and said comonomer is present in an amount of from about 1 % up to about 99%.

35. A process according to claim 34, wherein said comonomer is vinylidene chloride, acrylonitrile, 2-chloropropene, acrylic acid esters and maleic acid esters.

36. A process according to claim 25, comprising vinyl chloride, an initiator containing one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α-trihaloalkane, a perhaloalkane, a perfloroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof; a catalyst containing one or more of SO2- containing compounds, including Na₂S₂Q₄, H₂NC( = NH)S0₂H, H0CH₂S0₂Na, H0CH₂S0₃Na, Na₂S0₃, Na₂S₂0₅, Na₂S₂0₃, CH₃S0₂Na, C6H5S0₂Na, p-CH3C6H₄S0₂Na or a polydialkylamino-substituted unsaturated organic compound including (Me₂N)₂C = C(NMe₂)₂ and combinations thereof; a buffer, wherein said buffer is one or more of NaHCOs, Na₂HP04, NaH₂P0₄, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CHsCOOK, NH₄HCOs, (NH₄)₂HP0₄, NH₄H₂P0₄, CH3COONH4, and combinations thereof; and an electron shuttle, wherein said shuttle is a l,l'-dialkyl-4,4'-bipyrridinium dihalide

37. A process according to claim 28, wherein said halogen containing initiator is part of a polymer chain, including the chain ends of the said polymer.

38. A process according to claim 30, including said electron shuttle, wherein said shuttle is a l,l'-dialkyl-4,4'-bipyrridinium dihalide, and said electron shuttle is present in an amount from about 0.00001 to about 1 mole of shuttle per mole of catalyst.

39. A process according to claim 38, including said surfactant, wherein said surfactant is on or more of sodium dodecylsulfate, hydroxypropyl methylcellulose, 72.5% hydrolyzed polyvinyl acetate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, or combinations thereof, and said surfactant is present in an amount from about 10 to about 5000 parts per million w/w relative to halide containing monomer.

40. A viscosity modifier, flame retarding agent or a compatibilizing agent made by the process of claim 25.

41 . A process according to claim 25, wherein the molecular weight distribution of said composition is from about < 2.0 down to about < 1 .5.

42. A process according to claim 30, wherein said molecular weight distribution is from about <1 .5 down to about < 1 .1 .

43. A process according to claim 30, wherein said vinyl chloride monomer is dissolved in a solvent, said solvent comprising one or more of halogenated benzenes, linear and cyclic ethers, ketones, esters, alkanes, alcohols and combinations thereof, and wherein said solvent is present in an amount from about 25 to about 1000 parts by weight per 100 parts by weight of the vinyl chloride monomer.

44. A process according to claim 43, wherein said solvent is chlorobenzene, dichlorobenzene, trichlorobenzene, xylene, diphenylether, 1 ,2-dichloro ethane, tetrahydrofuran, dioxane, dimethylformamide, cyclohexanone, acetone, diethyloxalate, ethylhexylphtalate, dimethysulfoxide, methanol, ethanol, butanol or combinations thereof, and said solvent is present in an amount from about 1 to about 10 parts per volume of halide containing monomer.

45. A process according to claim 25, wherein the polymerization of said vinyl chloride monomer is carried out in water.

46. A process according to claim 30, wherein the polymerization of said vinyl chloride monomer is carried out in mixtures of water with chlorobenzene, dichlorobenzene, trichlorobenzene, xylene, diphenylether, 1 ,2-dichloroethane, tetrahydrofuran, dioxane, dimethylformamide, cyclohexanone, acetone, diethyloxalate, ethylhexylphtalate, dimethysulfoxide, methanol, ethanol, butanol or combinations thereof.

47. A polymeric composition comprising: a copolymer derived from a radical or a living radical polymerization of vinyl halide monomer or a structurally-related derivative and a comonomer known to copolymerize with vinyl chloride via a radical mechanism in the presence of: an initiator; a metal-free catalyst; and optionally, a buffer, an electron shuttle, a surfactant, and a solvent or water.

48. A composition according to claim 47, wherein said initiator is a halogen-containing initiator and said initiator contains one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α- trihaloalkane, a perhaloalkane, a perfloroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α- haloketone, an imidylhalide, or combinations thereof.

49. A composition according to claim 48, wherein said halogen is one or more of chlorine, bromine, or iodine, and said initiator is present in an amount from about 5000 to about 1 moles of halide-containing monomer per mole of initiating group.

50. A composition according to claim 49, wherein said initiator is iodoform, 1 -chloro-1 -iodoetane, or 1 -iodoperfluoroalkene.

no

51 . A composition according to claim 48, wherein said catalyst is a non-metal reducing, single electron transfer species.

52. A composition according to claim 51 , wherein said catalyst is sodium dithionite or formamidinesulfinic acid, said catalyst is present in an amount from about 0.01 to about 4 moles per mole of initiating group in the initiator, and said vinyl halide monomer is vinyl chloride.

53. A composition according to claim 51 , including said buffer, wherein said buffer includes one or more of NaHC0₃, Na₂HP0₄, NaH₂Pθ4, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CH3COOK, NH4HCO3, (NH₄)₂HP0₄, NH₄H₂P0₄, CH₃COONH₄ or combinations thereof, and said buffer is present in an amount from about 0.1 to about 5 moles of buffer per mole of catalyst.

54. A composition according to claim 41 , further comprising a comonomer, wherein said comonomer is an acrylate, a vinylidene halide, a 2-haloalkene, a methacrylate, an acrylonitrile, a methacrylonitrile, a vinyl halide, a styrene, an acrylamide, a methacrylamide, a vinyl ketone, an N-vinylpyrrolidinone, a vinyl acetate, a maleic acid ester, or combinations thereof, and said comonomer is present in an amount of from about 1 % up to about 99%.

55. A composition according to claim 54, wherein said comonomer is vinylidene chloride, acrylonitrile, 2-chloropropene, acrylic acid esters and maleic acid esters.

Ill

56. A composition according to claim 51 , including said electron shuttle, wherein said electron shuttle is a 1 ,1 '-dialkyl-4,4'- bipyridinium dihalide.

57. A composition according to claim 56, wherein said electron shuttle is one or more of 1 , 1 '-dimethyl-4,4'-bipyridinium dichloride, 1 , 1 '-d-n-octyl-4,4'-bipyridinium dibromide, or combinations thereof, and said electron shuttle is present in an amount from about 0.00001 to about 1 mole of shuttle per mole of catalyst.

58. A composition according to claim 51 , including said surfactant, wherein said surfactant is on or more of sodium dodecylsulfate, hydroxypropyl methylcellulose, 72.5% hydrolyzed polyvinyl acetate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, or combinations thereof, and said surfactant is present in an amount from about 10 to about 5000 parts per million w/w relative to halide containing monomer.

59. A composition according to claim 47, comprising vinyl chloride, an initiator containing one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α-trihaloalkane, a perhaloalkane, a perfloroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof; a catalyst containing one or more of an SO2- containing compound or a polydialkylamino-substituted unsaturated organic compound, or combinations thereof; a buffer containing one or more of NaHCOs, Na₂HP0₄, NaH₂P0₄, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CHsCOOK, NH₄HC0₃, (NH₄)₂HP0₄, NH₄H₂P0₄, CHsC00NH₄ or combinations thereof; an electron shuttle which is a 1 , 1 '-dialkyl-4,4'- bipyridinium dihalide; and a surfactant which is one or more of sodium dodecylsulfate, hydroxypropyl methylcellulose, 72.5% hydrolyzed polyvinyl acetate, polyoxyethylene (10) oleyl ether, polyoxyethylene (20) oleyl ether, or combinations thereof.

60. A composition according to claim 52, wherein the molecular weight distribution of said composition is from about <2.0 down to about <1 .5.

61 . A viscosity modifier, flame retarding agent, or compatibilizing agent containing the composition of claim 47.

62. A viscosity modifier, flame retarding agent, or compatibilizing agent containing the composition of claim 51 .

63. A viscosity modifier, flame retarding agent, or compatibilizing agent containing the composition of claim 53.

64. A polymeric composition comprising: a vinyl halide polymer derived from a radical polymerization of vinyl halide monomer in the presence of: an initiator; a catalyst; and optionally, a buffer, a surfactant and a solvent or water.

65. A polymeric composition according to claim 64, wherein said vinyl halide monomer is one or more of vinyl chloride, vinylidene chloride or 2-chloropropene.

66. A polymeric composition according to claim 64, wherein said initiator is a halogen containing initiator and said initiator contains one or more of a mono, di, tri or polyfunctional α,α-dihaloalkane, α,α,α-trihaloalkane, a perhaloalkane, a perfluoroalkyl halide, a polyfluoroalkyl halide, a benzyl halide, an allyl halide, a sulfonyl halide, an α-haloester, an α-halonitrile, an α-haloketone, an imidylhalide, or combinations thereof.

67. A polymeric composition according to claim 66, wherein said halogen is one or more of chlorine or bromine, and said initiator is present in an amount from about 5000 to about 1 moles of halide containing monomer per mole of initiating group.

68. A polymeric composition according to claim 67, wherein said initiator is bromoform, chloroform, carbon tetrabromide or carbon tetrachloride

69. A polymeric composition according to claim 66, wherein said catalyst is C0₂ ^" - radical anion forming species.

70. A polymeric composition according to claim 69, wherein said catalyst is present in an amount of from about 0.01 to about 4 moles per mole of initiating group in the initiator, and said catalyst is alkali metal or ammonium persulfate and alkali metal or ammonium formate in the ratio 1 : 1 .

71 . A polymeric composition according to claim 70, wherein said alkali metal is one or more of sodium or potassium

72. A polymeric composition according to claim 64, including said buffer, wherein said buffer includes one or more of NaHC0₃, Na₂HP0₄, NaH₂P0₄, CHsCOONa, KHCOs, K₂HP0₄, KH₂P0₄, CHsCOOK, NH₄HC0₃, (NH₄)₂HP0₄, NH₄H₂P0₄, CH₃COONH₄ or combinations thereof, and said buffer is present in an amount from about 0.1 to about 5 moles of buffer per mole of catalyst.