US20060025551A1 - Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin - Google Patents
Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin Download PDFInfo
- Publication number
- US20060025551A1 US20060025551A1 US11/219,903 US21990305A US2006025551A1 US 20060025551 A1 US20060025551 A1 US 20060025551A1 US 21990305 A US21990305 A US 21990305A US 2006025551 A1 US2006025551 A1 US 2006025551A1
- Authority
- US
- United States
- Prior art keywords
- weight
- vinyl
- acid
- comonomers
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 22
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title claims abstract description 11
- 239000007787 solid Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002118 epoxides Chemical class 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000007513 acids Chemical class 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 235000010350 erythorbic acid Nutrition 0.000 claims description 4
- 229940026239 isoascorbic acid Drugs 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- -1 methyl glycidyl Chemical group 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims description 2
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 2
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 4
- 230000000379 polymerizing effect Effects 0.000 claims 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- OUTQTRJBSUBFPJ-UHFFFAOYSA-N 1-(oxiran-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)C1CO1 OUTQTRJBSUBFPJ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
Definitions
- the invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymer solid resins and to the use thereof, in particular in coating resin compositions.
- Vinyl chloride copolymers containing epoxy groups are used as binders in coatings. Their use in heat-seal coatings, for example, for aluminum coating, should be singled out.
- Epoxy-containing vinyl chloride-vinyl acetate copolymers are well established but are obtainable only as solutions, for example in toluene and/or methyl ethyl ketone. For the user, this has the disadvantage that the choice of the solvent in which the coating resin is applied is greatly limited, for example to the solvent in which the coating resin is offered, or to solvents compatible therewith.
- an object of the invention is to provide epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins. This and other objects are achieved by a process in which vinyl chloride is copolymerized with epoxy group-containing comonomers and vinyl ester comonomers in the presence of aldehyde molecular weight regulators.
- the invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins obtainable by means of aqueous, free radical polymerization of a mixture comprising
- Suitable epoxide-containing vinyl monomers b) are, for example, methylglycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate.
- Glycidyl methacrylate (GMA) is preferred.
- Preferred vinyl ester monomers c) are those of carboxylic acids having 1 to 12 carbon atoms.
- Vinyl acetate is most preferred.
- Preferably from 5 to 15% by weight of the vinyl ester monomers c), in particular vinyl acetate, are copolymerized.
- Suitable further copolymerizable comonomers d) include one or more ethylenically unsaturated monomers from the group of acrylates or methacrylates of branched or straight-chain alcohols or diols having 1 to 18 carbon atoms, and ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof.
- Preferred monomers from the group consisting of acrylates or methacrylates are esters of straight-chain or branched alcohols having 1 to 15 carbon atoms.
- Particularly preferred methacrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate and 2-ethylhexyl acrylate.
- Methyl acrylate, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate are most preferred.
- Suitable ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride.
- the free radical polymerization is effected by means of suspension polymerization.
- the polymerization temperature is in general from 20° C. to 80° C.
- the initiation of the polymerization can be effected with the customary water-soluble or monomer-soluble initiators or redox initiator combinations.
- water-soluble initiators are the sodium, potassium and ammonium salts of peroxoydisulfuric acid.
- monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and tert-butyl peroxypivalate.
- the initiators are used in general in an amount of from 0.01 to 1.0% by weight, preferably from 0.1 to 0.5% by weight, based in each case on the total weight of the monomers.
- polymerization is effected in water in the presence of surface-active substances such as protective colloids and/or emulsifiers.
- Suitable protective colloids are, for example, partly hydrolyzed polyvinyl alcohols and cellulose ethers.
- Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, ester and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkylpolylglycol ethers or alkylarylpolyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
- anionic surfactants such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, ester and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as al
- 0.001 to 0.1% by weight preferably from 0.005 to 0.05% by weight of ascorbic acid and/or isoascorbic acid, based in each case on the total weight of the comonomers, are optionally added during or after the polymerization.
- Ascorbic acid is preferably used. The addition is preferably effected after the end of the monomer metering and before, during or after the removal of residual monomers.
- citric acid is also added in addition to ascorbic acid and/or isoascorbic acid is most preferred.
- the amount of citric acid is from 0.001 to 0.1% by weight, preferably from 0.005 to 0.05% by weight, based in each case on the total weight of the comonomers.
- regulating substances are used during the polymerization.
- the regulators are used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered separately or in a form premixed with reaction components.
- Suitable regulators are aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
- Polymerization is preferably effected in the presence of propionaldehyde.
- propionaldehyde Compared with other regulators such as, for example, trichloroethylene, propionaldehyde has the advantage that a regulating effect is achieved even with small amounts. It is therefore preferably added in an amount of from 0.02 to 5% by weight, based on the monomer, depending on the desired molecular weight.
- the monomers can be metered in together or can be initially introduced in portions and the remainder metered in after initiation of the polymerization.
- the meterings can be carried out separately (with respect to space and time), or some or all of the components to be metered can be metered in preemulsified form.
- postpolymerization can be effected for removing residual monomers with the use of known methods, for example by postpolymerization initiated by a redox catalyst.
- Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing inert entraining gases such as air, nitrogen or steam, through or over the reaction mixture.
- the epoxy-modified vinyl chloride-vinyl ester copolymers can be isolated from the aqueous dispersion in the form of solid resin by means of customary methods, by precipitation, filtration and subsequent drying, or by means of decanting and subsequent drying.
- the drying can be effected in a manner known to those skilled in the art, for example in a tumble drier, in a flow tube, in a fluidized bed, or in a cyclone drier.
- the epoxy-modified vinyl chloride-vinyl ester copolymers are distinguished by high blocking resistance up to 180° C., and by high chemical resistance to solvents, acids and bases.
- the epoxy-modified vinyl chloride-vinyl ester copolymers in the form of their solid resins are suitable, for example, as adhesives, in particular for the adhesive bonding of security features in banknotes or plastic cards, and as binders for coatings, for example for aluminum coatings.
- a copolymer comprising 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate was prepared by the suspension polymerization process, the comonomers having been completely initially introduced before initiation of the polymerization. After the end of the polymerization, the batch was let down to atmospheric pressure, and 0.05% by weight of ascorbic acid was added. Thereafter, demonomerization was effected and the copolymer was filtered, washed and dried. A white, flowable powder was obtained.
- a copolymer was prepared from 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate by the emulsion polymerization process. At the end of the reaction, the mixture was let down to atmospheric pressure and 0.02% by weight of ascorbic acid and 0.0025% by weight of citric acid, based in each case on the total weight of the comonomers and in each case as a 10% strength aqueous solution, were added to the batch. Thereafter, demonomerization was effected and the copolymer was precipitated, filtered, washed and dried. A white, flowable powder was obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/584,101 US7888429B2 (en) | 2003-03-06 | 2009-08-31 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10309857A DE10309857A1 (de) | 2003-03-06 | 2003-03-06 | Epoxy-modifizierte Vinylchlorid-Vinylester-Copolymer-Festharze |
| DE10309857.7 | 2003-03-06 | ||
| PCT/EP2004/002213 WO2004078806A1 (de) | 2003-03-06 | 2004-03-04 | Epoxy-modifizierte vinylchlorid-vinylester-copolymer-festharze |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2004/002213 Continuation WO2004078806A1 (de) | 2003-03-06 | 2004-03-04 | Epoxy-modifizierte vinylchlorid-vinylester-copolymer-festharze |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/584,101 Continuation US7888429B2 (en) | 2003-03-06 | 2009-08-31 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20060025551A1 true US20060025551A1 (en) | 2006-02-02 |
Family
ID=32891914
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/219,903 Abandoned US20060025551A1 (en) | 2003-03-06 | 2005-09-06 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
| US12/584,101 Expired - Lifetime US7888429B2 (en) | 2003-03-06 | 2009-08-31 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US12/584,101 Expired - Lifetime US7888429B2 (en) | 2003-03-06 | 2009-08-31 | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US20060025551A1 (de) |
| EP (1) | EP1599516B1 (de) |
| JP (1) | JP2006519885A (de) |
| CN (1) | CN100369945C (de) |
| AT (1) | ATE335019T1 (de) |
| DE (2) | DE10309857A1 (de) |
| ES (1) | ES2270356T3 (de) |
| WO (1) | WO2004078806A1 (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100256287A1 (en) * | 2007-12-03 | 2010-10-07 | Wacker Chemie Ag | Radically cross-linkable polymer compositions containing epoxy-functional copolymers |
| US8952096B2 (en) | 2008-12-10 | 2015-02-10 | Wacker Chemie Ag | Graft copolymers and use thereof as low-profile additives |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005041593A1 (de) * | 2005-09-01 | 2007-03-08 | Wacker Polymer Systems Gmbh & Co. Kg | Verfahren zur Herstellung von Vinylchlorid-Vinylacetat-Mischpolymerisaten in Form deren Festharze |
| JP5729286B2 (ja) * | 2010-12-24 | 2015-06-03 | 日信化学工業株式会社 | 塩化ビニル系樹脂及びその製造方法並びにインキ |
| CN103396750B (zh) * | 2013-07-16 | 2015-12-02 | 江苏斯德瑞克化工有限公司 | 水性粘胶剂的制备及金属/聚丙烯复合材料制作方法 |
| ES2835787T3 (es) * | 2017-08-07 | 2021-06-23 | Wacker Chemie Ag | Copolimeros de cloruro de vinilo, acetato de vinilo y ésteres vinílicos de cadena larga |
| CN107955108B (zh) * | 2017-10-26 | 2019-10-25 | 无锡洪汇新材料科技股份有限公司 | 一种环氧改性氯乙烯丙烯酸酯共聚乳液的制备方法 |
| CN109134736A (zh) * | 2018-06-21 | 2019-01-04 | 安徽大学 | 一种重防腐涂料用水性聚偏二氯乙烯-丙烯酸酯共聚胶乳及其制备方法 |
| CN114478893B (zh) * | 2021-12-29 | 2024-03-26 | 石河子大学 | 一种亲水性氯乙烯共聚树脂及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993034A (en) * | 1955-06-02 | 1961-07-18 | Swern Daniel | Copolymers of vinyl chloride and vinyl epoxystearate |
| US4345056A (en) * | 1976-07-02 | 1982-08-17 | Wacker-Chemie Gmbh | Process for suspension polymerization of vinyl chloride employing mixed protective colloids |
| US4693934A (en) * | 1984-06-08 | 1987-09-15 | Tdk Corporation | Magnetic recording medium for image recording |
| US4707411A (en) * | 1984-05-11 | 1987-11-17 | Nippon Zeon Co., Ltd. | Magnetic paint for magnetic recording media |
| US4900777A (en) * | 1981-10-06 | 1990-02-13 | Wacker-Chemie Gmbh | Process for the manufacture of aqueous copolymer dispersions and their use |
| US4970127A (en) * | 1986-10-20 | 1990-11-13 | Union Carbide Chemicals And Plastics Company Inc. | Novel vinyl chloride resins and compositions incorporating such resins |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53104684A (en) * | 1977-02-24 | 1978-09-12 | Shin Etsu Chem Co Ltd | Preparation of vinyl chloride polymer |
| DE3041887A1 (de) * | 1980-11-06 | 1982-06-09 | Henkel KGaA, 4000 Düsseldorf | Stabilisatorkombination fuer thermoplaste, insbesondere polymerisate auf basis von vinylchlorid sowie verfahren zur warmverformung derartiger polymerisate |
| BR8705574A (pt) * | 1986-10-20 | 1988-05-24 | Union Carbide Corp | Copolimero de cloreto de vinila adequado para ser usado como uma resina aglutinante para material particulado;e meio de gravacao magnetica |
| DE3829711A1 (de) * | 1988-09-01 | 1990-03-22 | Basf Ag | Polymerdispersionen und -loesungen enthaltend vinylchlorid-glycidylmethacrylat-copolymerisate, verfahren zur herstellung und ihre verwendung zur herstellung von bindemitteln auf dem lacksektor und von pulver |
| NO166189C (no) * | 1989-02-08 | 1991-06-12 | Norsk Hydro As | Tverrbundet termostabil polymer og fremstilling derav. |
| JPH0386744A (ja) * | 1989-08-30 | 1991-04-11 | Sekisui Chem Co Ltd | 塩化ビニル系合わせガラス用中間膜組成物及び合わせガラス用中間膜 |
| JP2849931B2 (ja) * | 1989-11-20 | 1999-01-27 | 日本ゼオン株式会社 | ペースト用塩化ビニル系重合体の製造方法 |
| JPH0489810A (ja) * | 1990-08-03 | 1992-03-24 | Shin Etsu Chem Co Ltd | 低重合度塩化ビニル系重合体の製造方法 |
| DE4124819A1 (de) * | 1991-07-26 | 1993-01-28 | Basf Ag | Waessrige polymerisatdispersionen |
| JPH07278209A (ja) * | 1994-04-12 | 1995-10-24 | Sekisui Chem Co Ltd | 塩化ビニル系重合体の製造方法 |
| JPH082154A (ja) * | 1994-06-17 | 1996-01-09 | Tokin Corp | 磁気ストライプカード及びその製造方法 |
| US5641845A (en) * | 1995-08-11 | 1997-06-24 | Libbey-Owens-Ford Co. | Copolymers of vinyl chloride, allyl glycidyl ether, and a vinyl ester and method of making the same |
| JPH10168104A (ja) * | 1996-12-10 | 1998-06-23 | Mitsubishi Chem Corp | 塩化ビニル系単量体の重合方法 |
| JP3445457B2 (ja) * | 1996-12-25 | 2003-09-08 | タキロン株式会社 | 難燃性塩化ビニル樹脂成形体 |
| DE19733156A1 (de) * | 1997-07-31 | 1999-02-04 | Wacker Chemie Gmbh | Vernetzbare, in Wasser redispergierbare Pulverzusammensetzung |
| JPH11140256A (ja) * | 1997-11-04 | 1999-05-25 | Tosoh Corp | ペースト加工用球状塩化ビニル系ブレンド樹脂、その製造方法およびそれよりなるペースト加工用塩化ビニル樹脂組成物 |
| EP0989162A4 (de) * | 1998-03-31 | 2002-11-06 | Daicel Chem | Thermoplastische harzzusammensetzung, wässrige zusammensetzung, wärmeempfindliches druckempfindliches klebemittel und wärmeempfindliche klebeschicht |
| JP2001139698A (ja) * | 1999-11-17 | 2001-05-22 | Shin Etsu Chem Co Ltd | 屋外建材用塩化ビニル系樹脂硬質成形品 |
| JP3967173B2 (ja) * | 2001-05-09 | 2007-08-29 | 株式会社クレハ | ポリ塩化ビニリデン系樹脂組成物及びその製造方法 |
-
2003
- 2003-03-06 DE DE10309857A patent/DE10309857A1/de not_active Withdrawn
-
2004
- 2004-03-04 WO PCT/EP2004/002213 patent/WO2004078806A1/de active IP Right Grant
- 2004-03-04 EP EP04717093A patent/EP1599516B1/de not_active Expired - Lifetime
- 2004-03-04 AT AT04717093T patent/ATE335019T1/de not_active IP Right Cessation
- 2004-03-04 CN CNB2004800061527A patent/CN100369945C/zh not_active Expired - Lifetime
- 2004-03-04 JP JP2006500049A patent/JP2006519885A/ja active Pending
- 2004-03-04 ES ES04717093T patent/ES2270356T3/es not_active Expired - Lifetime
- 2004-03-04 DE DE502004001101T patent/DE502004001101D1/de not_active Expired - Lifetime
-
2005
- 2005-09-06 US US11/219,903 patent/US20060025551A1/en not_active Abandoned
-
2009
- 2009-08-31 US US12/584,101 patent/US7888429B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2993034A (en) * | 1955-06-02 | 1961-07-18 | Swern Daniel | Copolymers of vinyl chloride and vinyl epoxystearate |
| US4345056A (en) * | 1976-07-02 | 1982-08-17 | Wacker-Chemie Gmbh | Process for suspension polymerization of vinyl chloride employing mixed protective colloids |
| US4900777A (en) * | 1981-10-06 | 1990-02-13 | Wacker-Chemie Gmbh | Process for the manufacture of aqueous copolymer dispersions and their use |
| US4707411A (en) * | 1984-05-11 | 1987-11-17 | Nippon Zeon Co., Ltd. | Magnetic paint for magnetic recording media |
| US4693934A (en) * | 1984-06-08 | 1987-09-15 | Tdk Corporation | Magnetic recording medium for image recording |
| US4970127A (en) * | 1986-10-20 | 1990-11-13 | Union Carbide Chemicals And Plastics Company Inc. | Novel vinyl chloride resins and compositions incorporating such resins |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100256287A1 (en) * | 2007-12-03 | 2010-10-07 | Wacker Chemie Ag | Radically cross-linkable polymer compositions containing epoxy-functional copolymers |
| US8952096B2 (en) | 2008-12-10 | 2015-02-10 | Wacker Chemie Ag | Graft copolymers and use thereof as low-profile additives |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1599516A1 (de) | 2005-11-30 |
| US20090321016A1 (en) | 2009-12-31 |
| WO2004078806A1 (de) | 2004-09-16 |
| ES2270356T3 (es) | 2007-04-01 |
| US7888429B2 (en) | 2011-02-15 |
| EP1599516B1 (de) | 2006-08-02 |
| ATE335019T1 (de) | 2006-08-15 |
| JP2006519885A (ja) | 2006-08-31 |
| DE10309857A1 (de) | 2004-09-23 |
| DE502004001101D1 (de) | 2006-09-14 |
| CN100369945C (zh) | 2008-02-20 |
| CN1756778A (zh) | 2006-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7888429B2 (en) | Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin | |
| JP2831317B2 (ja) | コポリマーおよび保護コロイドを含む水性媒質中に再分散可能な化学組成物、その水性ポリマー分散体、その製造方法およびその使用方法 | |
| US7915364B2 (en) | Method for producing vinyl chloride-vinyl acetate copolymers in the form of their solid resins | |
| US3644262A (en) | Process for increasing the ethylene content of vinyl acetate-ethylene emulsion copolymers | |
| US20030114583A1 (en) | Hydrophobicized copolymers | |
| US6534177B2 (en) | Crosslinkable polymer composition | |
| US5296532A (en) | Adhesive compositions containing aqueous copolymer dispersions and acid metal salts or free acids | |
| US7655741B2 (en) | Thermostable vinylchloride mixed polymers | |
| US4665142A (en) | Emulsion polymers free from emulsifiers and protective colloids, a process for their preparation and their use | |
| US3352838A (en) | Methylolated urea and melamine etherified with butanol and polyethyleneglycol as emulsion polymerization agents | |
| WO2018105962A1 (ko) | 염화비닐계 수지 조성물의 제조 방법 | |
| TWI343397B (en) | Solid polyvinyl ester and the preparing process and use of the same | |
| US6716941B2 (en) | High solids ethylene-vinyl acetate latex | |
| EP2756012B1 (de) | Vinylacetat/vinyl 3,5,5-trimethylhexanoat-copolymer-binderharze | |
| JP3121818B2 (ja) | 水性アクリルポリマー分散液及びその製造方法 | |
| US7358297B2 (en) | Preparation of multimodal polymer dispersions using polymeric stabilizer, and use thereof | |
| WO2000022016A1 (en) | Latex polymer compositions | |
| JP3420920B2 (ja) | 木工用接着剤 | |
| US4098985A (en) | Ester copolymers cross-linkable under acid and alkaline conditions | |
| CN111770974A (zh) | 粘合剂组合物 | |
| JPH01144402A (ja) | 非水性分散重合 | |
| JPS6011502A (ja) | 合成樹脂水分散体 | |
| JPH0331350A (ja) | 安定性と耐久性の優れたビニルハライドラテックス組成物 | |
| JPS61278512A (ja) | 塩化ビニル共重合体の製造法 | |
| IE45992B1 (en) | Preparation of dispersions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: WACKER POLYMER SYSTEMS GMBH & CO. KG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAISER, STEPHAN;WEBER, KARL;REEL/FRAME:016646/0640;SIGNING DATES FROM 20050825 TO 20050906 Owner name: VINNOLIT GMBH & CO. KG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KAISER, STEPHAN;WEBER, KARL;REEL/FRAME:016646/0640;SIGNING DATES FROM 20050825 TO 20050906 |
|
| AS | Assignment |
Owner name: WACKER CHEMIE AG, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WACKER POLYMER SYSTEMS GMBH & CO. KG;REEL/FRAME:021603/0608 Effective date: 20080801 Owner name: WACKER CHEMIE AG,GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WACKER POLYMER SYSTEMS GMBH & CO. KG;REEL/FRAME:021603/0608 Effective date: 20080801 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |