WO2003002621A1 - Polymerisation radicalaire d'un halide vinylique - Google Patents

Polymerisation radicalaire d'un halide vinylique Download PDF

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Publication number
WO2003002621A1
WO2003002621A1 PCT/US2002/020588 US0220588W WO03002621A1 WO 2003002621 A1 WO2003002621 A1 WO 2003002621A1 US 0220588 W US0220588 W US 0220588W WO 03002621 A1 WO03002621 A1 WO 03002621A1
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initiator
catalyst
halide
mmol
vinyl chloride
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PCT/US2002/020588
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English (en)
Inventor
Virgil Percec
Anatoliy V. Popov
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University Of Pennsylvania
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Priority claimed from US09/893,201 external-priority patent/US6838535B2/en
Application filed by University Of Pennsylvania filed Critical University Of Pennsylvania
Priority to MXPA03011993A priority Critical patent/MXPA03011993A/es
Priority to EP02749697A priority patent/EP1406935A1/fr
Publication of WO2003002621A1 publication Critical patent/WO2003002621A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride

Definitions

  • 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.
  • 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.
  • PVC poly(vinyl chloride)
  • 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 S0 2 group.
  • the process can be accelerated by electron shuttles such as alkyl viologens.
  • 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.
  • 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.
  • 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.
  • the halide initiators include, but are not limited to various activated mono, di, tri and polyfunctional ⁇ , ⁇ -dihaloalkanes, , ⁇ , ⁇ -trihaloalkanes, perhaloalkanes, perfloroalkyl halides, benzyl halides, allyl halides, sulfonyl halides, -haloesters, ⁇ -halonitriles, ⁇ -haloketones, imidyl halides, or combinations thereof.
  • 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.
  • preferred initiators include chlorine, bromine and thiocyanate containing compounds, with iodide initiators being desirable.
  • 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 R ⁇ R 2 R 3 C-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.
  • EWG electron withdrawing group
  • R substituents can be H, alkyl chains including polymer chains, electron withdrawing groups and combinations thereof.
  • the preferred iodine containing initiators include: l-CH 2 -Ph-CH 2 -l, CH 3 -CH(CI)-I, CH 2
  • halide initiators 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.
  • 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.
  • the metals be in their zero oxidation state for the metal catalyzed propagation and therefore, living radical polymerization to occur.
  • 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.
  • Fe(0) is used as catalyst for the polymerization of vinyl chloride
  • chlorine and bromine based initiators are suitable.
  • the preferred initiators for Fe(0) are for example, the active (CH 3 ) 2 (COOEt)-Br, CH 3 -CH(Ph)-Br, F-Ph-S0 2 -Cl, as well as the -CH 2 - (CH 3 )C(COOMe)-CI chain end of PMMA synthesized by metal catalyzed living radical polymerization.
  • titanium-based catalysts such as TiCp 2 CI 2
  • 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.
  • 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.
  • 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), tri
  • ligands and 1 , 10-phenantroline are also appropriate for Fe-based catalysts.
  • other ligands such as CO, acetylacetonate, or terpyridine may be used.
  • the use of a ligand is not necessary for TiCp 2 CI 2 but is preferred for Cu and Fe based catalysts.
  • 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.
  • 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.
  • 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.
  • solvents such as organic fluids or mixtures of organic fluids may be utilized.
  • 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.
  • 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 plasticiser
  • 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.
  • the living free radical polymerization of vinyl chloride can be carried out in the absence of solvent.
  • the polymerization is generally carried out in bulk and the other reaction conditions set forth hereinabove are generally suitable.
  • 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.
  • an emulsifier such as sodium dodecylsulfate (NaDDS) is optional.
  • NaDDS sodium dodecylsulfate
  • 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.
  • 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.
  • the halide initiator can accept one electron and then release X " forming an initiating radical R ⁇
  • Such electron-accepting radical precursors include, but are not limited to, various activated mono, di, tri and polyfunctional activated halides. These include ⁇ , ⁇ -dihaloalkanes, ⁇ , ⁇ , ⁇ -trihaloalkanes, perhaloalkanes, perfluoroalkyl halides, polyfluoroalkyl halides, ⁇ -haloesters, ⁇ - halonitriles, ⁇ -haloketones, benzyl halides, sulfonyl halides, imidyl halides, or combinations thereof.
  • activated mono, di, tri and polyfunctional activated halides include ⁇ , ⁇ -dihaloalkanes, ⁇ , ⁇ , ⁇ -trihaloalkanes, perhaloalkanes, perfluoroalkyl halides, polyfluoroalkyl halides, ⁇ -haloesters, ⁇ - halonitriles, ⁇ -haloketone
  • 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.
  • preferred initiators are one electron accepting radical precursors including chlorine and bromine, with iodine initiators being desirable.
  • the system sodium persulfate - sodium formate (Na 2 S 2 0s - HCOONa, which form C0 2 " - 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, CBr 4 .
  • 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.
  • 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 S0 2 group and polydialkylamino-substituted unsaturated organic compounds.
  • (Me 2 N) 2 C C(NMe 2 ) 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.
  • 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, Na 2 HP0 4 , NaH 2 P0 4 , CHsCOONa or the potassium or ammonium salts thereof, including KHCOs, K 2 HP0 4 , KH 2 P0 4 , CHsCOOK, NH4HCO3, (NH 4 ) 2 HP0 4 , NH 4 H 4 P0 4 , CH 3 C00NH 4 , and the like.
  • 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.
  • 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.
  • shuttles examples include, but are not limited to, 1 ,1 '-dimethyl-4,4'- bipyridinium dichloride, methyl viologen (MV 2+ ), 1 ,1 '-di-n-octyl-4,4'- bipyridinium dibromide, octyl viologen (OV 2+ ), and the like.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • a surfactant is optional.
  • 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).
  • NaDDS sodium dodecylsulfate
  • Methodhocel ® F50 hydroxypropyl methylcellulose
  • Alcotex ® 72.5 polyoxyethylene(I O) oleyl ether
  • Brij ® 97 polyoxyethylene(20) oleyl ether
  • Brij ® 98 polyoxyethylene(20) oleyl ether
  • 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.
  • 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.
  • 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.
  • Table 6 Selected Exampl es of the Room Temperature Polymerization of Vinyl Chloride Catalyzed by Copper Catalysts in Water, Solvents and Mixtures Thereof.
  • Table 1 presents selected examples of Fe(0) catalyzed VC polymerization.
  • Examples 1 to 9 describe the initiation performed from ⁇ -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 ⁇ -cyanoesters and example 19 describes the use of sulfonyl halides as initiators.
  • the polymerization may be performed in o-DCB, THF or DMF.
  • 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 TiCp 2 CI 2 catalyzed polymerization of VC initiated from various halides.
  • TiCp ⁇ C catalyzes VC polymerization only to very low conversion.
  • Polymers can be obtained in the presence of ⁇ -haloesters (examples 21 to 25), benzy halides and pseudohalides (examples 26 to 31 ), ⁇ -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).
  • 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.
  • CuBr can catalyzed VC polymerization initiated from ⁇ -haloesters (examples 37 and 38).
  • More reactive Cu(l) species such as CuC ⁇ C-Ph, CuSPh or Cu 2 Te (examples 39, 40 and 46) can catalyze VC polymerization even in the presence of bpy as ligand.
  • 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 ⁇ - cyanohalides (examples 51 and 52), ⁇ -haloesters (examples 57-59, 61 -66 and 72-74) and various benzyl halides such as ⁇ , ⁇ '-dichloro-p- xylene (examples 54-56), ⁇ , ⁇ '-dibromo-p-xylene (example 70) 1 - bromo-1 -phenylethane (examples 68 and 69) and 1 ,2,4,5- tetrakisbromomethyl benzene (example 60, star polymer), ⁇ , ⁇ '-diiodo- /7-xylene (examples 1 18 to 137).
  • chloro, bromo and iodo initiators such as ⁇ - cyano
  • 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 ).
  • Table 5 presents miscellaneous examples of metal catalyzed VC polymerization. It was observed that ⁇ -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. ⁇ - 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.
  • activating ligands such as TREN
  • Cu(0) and its derivatives are successful in polymerizing VC at room temperature.
  • 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, Cu 2 Te/TREN and combinations thereof.
  • 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.
  • 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 Na 2 S 2 ⁇ 4-catalyzed LRP of VC initiated with iodoform in H 2 0/THF. Examples 1 - 22 with the same water-THF ratio 2/1 are plotted in Figure 1 . The two rate constants are observed.
  • k P ⁇ 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.
  • Mn is consistent with Mth as for a living process.
  • Table 8 presents room temperature Na 2 S 2 0 4 -catalyzed LRP of VC initiated with iodoform in H 2 0/THF in the presence of surfactant Brij ® 98.
  • H 2 0/THF ratios both 2/1 and 7/3.
  • Amount of the surfactant varies from 2080 to 16640 ppm w/w relative to VC.
  • Table 9 presents results of the room temperature Na 2 S 2 U4- catalyzed LRP of VC initiated with iodoform in H 2 0/THF in the presence of electron shuttle OV 2+ and surfactant Brij ® 98. All other factors being equal, decreasing of OV 2+ 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.
  • the rate constant of emulsion polymerizationand k ⁇ 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.
  • 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 Na 2 S 2 O4- catalyzed LRP of VC initiated with iodoform in H2O/THF in the presence of electron shuttle MV 2+ 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 MV 2+ (experiment 101 ) lows the conversion (36%) and shows an increase in polydispersity (1 .73) in comparison with lower amounts of methyl viologen (experiments 89,
  • the results of the experiments are plotted in Figure 7. Both k P ⁇ 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 OV 2+ or NaDDS reaction occurs there is no dithionite-catalyzed reaction in dry THF.
  • Different halogen containing compounds, other than iodoform, in conjunction with Na 2 S 2 0 4 can initiate VC polymerization (experiments 143, 144, 145, 146, 149) both in the presence of electron shuttle and surfactant and without them.
  • the C0 2 " - radical anion precursor Na 2 S 2 U8 - HCOONa is active in conjunction with bromo- or chloro- containing initiators (experiments 1 51 , 1 52, 1 62, 1 63).
  • Different S0 2 containing compounds other than Na 2 S 2 ⁇ 4 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.
  • 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 ( ⁇ , ⁇ ⁇ ), 90°C (v, ⁇ , + ) and 1 30°C ( ⁇ , ⁇ , 5).
  • Figure 4 The dependence of molecular weight ( ⁇ ) and molecular weight distribution ( ⁇ ) 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).
  • NaDDS sodium dodecylsulfate
  • 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 ⁇ m, 50 ⁇ and 10 ⁇ m, 10 4 ⁇ ) 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:
  • 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.
  • vinyl chloride 5 mL, 0.072 mol
  • solvent ortho-dichlorobenzene (o-DCB)
  • initiator ethyl 2-bromoisobutyrate, 223 mg, 1 .1 2 mmol
  • catalyst Fe(0), 40 mg, 0.7 mmol
  • ligand
  • 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 (TiCp 2 CI 2 , 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.
  • 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.
  • 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.
  • 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-(CH 2 ) ⁇ - SOsNa, (NaDDS, sodium dodecylsulfate), 21 mg, 0.072 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon.
  • 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-(CH 2 )n- S ⁇ 3Na, (NaDDS, sodium dodecylsulfate), 104 mg, 0.36 mmol) was degassed by three freeze-vacuum pump-thaw cycles and filled with argon.
  • 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 ( ⁇ , ⁇ '-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.
  • TREN tris(2-aminoethyl)amine
  • 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 ( ⁇ , ⁇ '-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.
  • vinyl chloride 5 mL, 0.072 mol
  • solvent o-DCB, 10 mL
  • initiator ⁇ , ⁇ '-diiodo-p- xylene, 50 mg, 0.14 mmol
  • catalyst copper, 36 mg, 0.
  • 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 ( ⁇ , ⁇ '-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- l butylpyridine, 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.
  • 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.
  • 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.
  • 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 (Na 2 S 2 0 4 , 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
  • 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).
  • 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.
  • 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
  • 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 (Na 2 S 2 0s, 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).
  • Example 1 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 Na 2 S 2 0s, 102.4 mg, 0.43 mmol and HCOONa, 29.2 mg, 0.43 mmol
  • buffer NaHCOs, 40.1 mg, 0.48 mmol
  • precondensed VC 3 mL, 0.043 mol
  • 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.
  • 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 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.
  • 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
  • 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 (Na 2 S 2 0 , 75.6 mg, 0.43 mmol), buffer (NaHC0 3 , 40.1 mg, 0.48 mmol), optional electron shuttle (OV 2+ , 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.

Abstract

L'invention concerne un procédé de polymérisation vivante permettant de préparer un poly(chlorure de vinyle) (PVC) à poids moléculaire et répartition de poids moléculaire commandés. La réaction de polymérisation peut être déclenchée par divers initiateurs de polyhalocarbure associés à des réactifs de transfert d'électron de réduction simple non métallique utilisés comme catalyseurs et accélérés à l'aide d'un agent de transfert d'électrons. Le procédé s'effectue à température ambiante dans de l'eau ou dans un milieu solvant non organique. La polymérisation permet d'obtenir un PVC à poids moléculaire et à répartition de poids moléculaire étroite commandés. On utilise, entre autres, des compositions polymères contenant un halogène comme modificateurs de viscosité, modificateurs d'impact et compatibiliseurs.
PCT/US2002/020588 2001-06-27 2002-06-27 Polymerisation radicalaire d'un halide vinylique WO2003002621A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
MXPA03011993A MXPA03011993A (es) 2001-06-27 2002-06-27 Polimerizacion por radicales del haluro de vinilo.
EP02749697A EP1406935A1 (fr) 2001-06-27 2002-06-27 Polymerisation radicalaire d'un halide vinylique

Applications Claiming Priority (3)

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US09/893,201 US6838535B2 (en) 2001-03-23 2001-06-27 Process for the living radical polymerization of chlorine containing monomers
US09/893,201 2001-06-27
US10/179,584 2002-06-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006080928A1 (fr) * 2005-01-26 2006-08-03 University Of Pennsylvania Polymérisation radicalaire vivante de monomères acryliques et halogénés et formation de copolymères séquencés à partir de cette polymérisation
EP2551284A1 (fr) 2011-07-25 2013-01-30 Ercros, S.A. Procédé de préparation de copolymères statitistiques à partir d'halogénures de vinyle et d'acrylates
WO2021161851A1 (fr) * 2020-02-14 2021-08-19 Ａｇｃ株式会社 Procédé de production d'un composé contenant de l'iode et polymère

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB674060A (en) * 1949-04-08 1952-06-18 Arthur William Barnes Improvements in and relating to polymerisation processes
US2831844A (en) * 1955-09-08 1958-04-22 Us Rubber Co Polymerization of vinyl chloride
GB1099391A (en) * 1964-01-08 1968-01-17 Kureha Chemical Ind Co Ltd Novel peroxydicarbonate ester and its use in the polymerization of vinyl chloride
NL6906754A (fr) * 1968-05-03 1969-11-05
NL7201105A (fr) * 1971-01-28 1972-08-01
US4425651A (en) 1980-09-25 1984-01-10 W. C. Heraeus Gmbh Ion laser with gas discharge vessel
EP0617057A1 (fr) 1993-03-22 1994-09-28 The Geon Company Polymérisation radicalaire "pseudo-vivante"
US5455319A (en) 1993-03-22 1995-10-03 The Geon Company Process for polymerizing vinyl chloride polymers with iodinated chain transfer agents
WO1997013792A1 (fr) 1995-10-06 1997-04-17 Commonwealth Scientific And Industrial Research Organisation Regulation du poids moleculaire et de la valence fonctionnelle des groupes terminaux dans des polymeres
JPH10130306A (ja) * 1996-10-29 1998-05-19 Asahi Glass Co Ltd 塩素含有ポリマーの製造法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB674060A (en) * 1949-04-08 1952-06-18 Arthur William Barnes Improvements in and relating to polymerisation processes
US2831844A (en) * 1955-09-08 1958-04-22 Us Rubber Co Polymerization of vinyl chloride
GB1099391A (en) * 1964-01-08 1968-01-17 Kureha Chemical Ind Co Ltd Novel peroxydicarbonate ester and its use in the polymerization of vinyl chloride
NL6906754A (fr) * 1968-05-03 1969-11-05
NL7201105A (fr) * 1971-01-28 1972-08-01
US4425651A (en) 1980-09-25 1984-01-10 W. C. Heraeus Gmbh Ion laser with gas discharge vessel
EP0617057A1 (fr) 1993-03-22 1994-09-28 The Geon Company Polymérisation radicalaire "pseudo-vivante"
US5455319A (en) 1993-03-22 1995-10-03 The Geon Company Process for polymerizing vinyl chloride polymers with iodinated chain transfer agents
WO1997013792A1 (fr) 1995-10-06 1997-04-17 Commonwealth Scientific And Industrial Research Organisation Regulation du poids moleculaire et de la valence fonctionnelle des groupes terminaux dans des polymeres
JPH10130306A (ja) * 1996-10-29 1998-05-19 Asahi Glass Co Ltd 塩素含有ポリマーの製造法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7345127B2 (en) 2001-03-23 2008-03-18 University Of Pennsylvania Living radical polymerization of halogen-containing and acrylic monomers and the formation of block copolymers therefrom
US7470762B2 (en) 2001-03-23 2008-12-30 University Of Pennsylvania Living radical polymerization of acrylic monomers and the formation of block copolymers therefrom
WO2006080928A1 (fr) * 2005-01-26 2006-08-03 University Of Pennsylvania Polymérisation radicalaire vivante de monomères acryliques et halogénés et formation de copolymères séquencés à partir de cette polymérisation
EP2551284A1 (fr) 2011-07-25 2013-01-30 Ercros, S.A. Procédé de préparation de copolymères statitistiques à partir d'halogénures de vinyle et d'acrylates
WO2013014158A1 (fr) 2011-07-25 2013-01-31 Ercros, S.A. Procédé pour la préparation de copolymères statistiques de monomères halogénure de vinyle et acrylate
US20140171609A1 (en) * 2011-07-25 2014-06-19 Ercros, S.A. Process for the preparation of random copolymers of vinyl halide and acrylate monomers
WO2021161851A1 (fr) * 2020-02-14 2021-08-19 Ａｇｃ株式会社 Procédé de production d'un composé contenant de l'iode et polymère

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