CN111164117B - 氯乙烯、乙酸乙烯酯和长链乙烯基酯的共聚物 - Google Patents
氯乙烯、乙酸乙烯酯和长链乙烯基酯的共聚物 Download PDFInfo
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- CN111164117B CN111164117B CN201780093643.7A CN201780093643A CN111164117B CN 111164117 B CN111164117 B CN 111164117B CN 201780093643 A CN201780093643 A CN 201780093643A CN 111164117 B CN111164117 B CN 111164117B
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- Prior art keywords
- vinyl
- weight
- monomer units
- vinyl chloride
- copolymers
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920001577 copolymer Polymers 0.000 title claims abstract description 29
- 229920001567 vinyl ester resin Polymers 0.000 title claims abstract description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- -1 card Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 3
- 239000000976 ink Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 150000003857 carboxamides Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 21
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 21
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 21
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 8
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
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- 239000003995 emulsifying agent Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical group 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000937 dynamic scanning calorimetry Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- WNIJCODJYBZSMF-UHFFFAOYSA-N ethenyl dodecanoate 2-ethenyldodecanoic acid Chemical compound CCCCCCCCCCCC(=O)OC=C.CCCCCCCCCCC(C=C)C(O)=O WNIJCODJYBZSMF-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-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
- 239000002966 varnish Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-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
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- 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
- C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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Abstract
本发明涉及氯乙烯、乙酸乙烯酯与一种或多种具有3至18个碳原子的直链或支化烷基羧酸的长链乙烯基酯的共聚物,其特征在于,其包含35‑80重量%的氯乙烯单体单元,1‑30重量%的乙酸乙烯酯单体单元和10‑64重量%的长链乙烯基酯单体单元,重量%的数值是基于共聚单体的总重量,并且重量%的数值在每种情况下相加为100重量%。
Description
本发明涉及氯乙烯、乙酸乙烯酯和一种或多种具有3至18个碳原子的直链或支化的烷基羧酸的长链乙烯基酯的共聚物,涉及通过自由基聚合的制备,并且涉及由此获得的共聚物的用途。
氯乙烯和乙烯基酯的共聚物是现有技术中已知的,并且可用于各种应用中:作为油漆和印刷油墨的粘合剂;用于浸渍和涂布纸、卡片、纺织品,无纺布,金属,矿物表面,木材和塑料;作为用于生产可热封和RF可焊接膜的涂料。
公开的说明书DE 1 745 555涉及一种制备氯乙烯、乙酸乙烯酯和长链乙烯基酯的共聚物的水分散体的方法。为了改善水分散体和由这些共聚物获得的聚合物膜的稳定性,建议使用由保护性胶体、阴离子乳化剂和非离子乳化剂组成的三元分散剂混合物而进行制备。公开的说明书DE 1 745 563推荐使用由聚乙烯基吡咯烷酮、羟基烷基纤维素和非离子乳化剂组成的三元分散剂混合物而制备该共聚物。
公开的说明书DE 2206593建议通过同样使用特定的分散剂,即纤维素醚与酯或酮的组合来改善氯乙烯-乙酸乙烯酯共聚物的性能。公开的说明书DE 2409800描述了在氯乙烯-乙酸乙烯酯共聚物的情况下,通过不饱和羧酸的共聚而改善了金属粘合性。
公开的说明书DE 2 364 057的主题是通过诸如乙酸乙烯酯的乙烯基酯的共聚而改善氯乙烯和马来酸酐的本体聚合物的溶解性和热稳定性。EP 0 177 956 A2描述了通过长链乙烯基酯的共聚而改善氯乙烯聚合物的可加工性,其中使乙烯基酯共聚以降低熔融粘度,并且使用硫醇链转移剂降低分子量。由EP 0 391 398 A1已知,通过用叔碳酸(Versaticacid)的乙烯基酯代替乙酸乙烯酯而改善氯乙烯-乙酸乙烯酯共聚物的热稳定性。
专利EP 1 599 515 B1描述了通过与含环氧化物的共聚单体在羟基羧酸的存在下进行共聚来制备热稳定的氯乙烯共聚物。
目前可获得的氯乙烯-乙酸乙烯酯共聚物在被加工时在较低极性的溶剂中的溶解度并不令人满意,其中所述溶剂例如芳族化合物、二醇酯或二醇醚。此外,期望改善对金属表面例如铝或塑料表面的粘附性。用目前可市购的氯乙烯-乙酸乙烯酯共聚物而获得的涂层的耐水性和复合材料的密封接缝强度同样需要改进。
本发明的主题是氯乙烯、乙酸乙烯酯和一种或多种具有3至18个碳原子的直链或支化烷基羧酸的长链乙烯基酯的共聚物,其特征在于它们包含35-80重量%的氯乙烯单体单元,1-30重量%的乙酸乙烯酯单体单元和10-64重量%的长链乙烯基酯单体单元,重量%的数值是基于共聚单体的总重量,重量%的数值在每种情况下相加为100重量%。
优选的共聚物具有50-75重量%的氯乙烯单体单元,5-25重量%的乙酸乙烯酯单体单元和10-55重量%的长链乙烯基酯的单体单元。特别优选的共聚物具有55-75重量%的氯乙烯单体单元,5-25重量%的乙酸乙烯酯单体单元和10-30重量%的月桂酸乙烯酯。
优选的具有3至18个碳原子的直链或支化烷基羧酸的长链乙烯基酯为丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、以及具有5至13个碳原子的α-支化的一元羧酸的乙烯基酯,其实例为新戊酸乙烯酯、VeoVa9R、VeoVa10R或VeoVa11R(商品名Hexion)。特别优选月桂酸乙烯酯(Wacker Chemie的商品名是VersaR 12)和具有9至10个碳原子的α-支化的一元羧酸的乙烯基酯(VeoVa9R和VeoVa10R)。最优选月桂酸乙烯酯(十二烷酸乙烯酯)。
任选,额外可以使至多10重量%,优选0.1-10重量%,更优选0.1-2.0重量%的官能共聚单体进行共聚。官能共聚单体的实例是烯键式不饱和一元羧酸和二元羧酸,优选丙烯酸、甲基丙烯酸、富马酸、衣康酸、巴豆酸和马来酸、以及马来酸酐;烯键式不饱和羧酰胺和腈,优选丙烯酰胺和丙烯腈;烯键式不饱和磺酸和/或其盐,优选乙烯基磺酸、2-丙烯酰胺基-2-甲基丙磺酸;含环氧化物的共聚单体,例如甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯、烯丙基缩水甘油醚、乙烯基缩水甘油醚,优选甲基丙烯酸缩水甘油酯。
这里,以重量%计的数值基于共聚单体的总重量,并且在每种情况下加起来为100重量%。
通过自由基引发的在本体中、在非水溶剂中或在水性介质中的聚合,借助悬浮聚合、乳液聚合、微悬浮聚合或微乳液聚合来制备共聚物。在溶液聚合的情况下,使用有机溶剂,例如乙酸乙酯或丙酮。优选在水性介质中的聚合方法,特别优选悬浮聚合和乳液聚合。聚合温度通常为20℃至85℃。聚合可以使用特定聚合方法常用的水溶性或单体可溶性的引发剂或氧化还原引发剂组合而进行引发。这些引发剂/组合是技术人员已知的。在每种情况下基于共聚单体的总重量,这些引发剂通常的用量为0.01至1.0重量%,优选0.1至0.5重量%。
如所述特别优选的悬浮和乳液聚合方法包括在表面活性物质例如保护性胶体和/或乳化剂的存在下在水中进行聚合。合适的保护性胶体例如为部分皂化和完全皂化的聚乙烯醇、纤维素及其羧甲基、甲基、羟乙基、羟丙基衍生物,淀粉和淀粉衍生物,(甲基)丙烯酸烷基酯和(甲基)丙烯酸OH-烷基酯的共聚物。优选的聚乙烯醇为部分皂化的聚乙烯醇,其水解度为70-95mol%,在4%水溶液中的粘度为1至30mPas(20℃下,方法,DIN 53015)。优选的纤维素醚是羟丙基-甲基纤维素。优选不使用聚乙烯吡咯烷酮。合适的乳化剂是阴离子、阳离子和非离子乳化剂,实例是阴离子表面活性剂,例如链长为8至18个碳原子的烷基硫酸盐、具有8至18个碳原子的烷基或烷基芳基磺酸盐、磺基琥珀酸与一元醇或烷基酚的全酯和单酯、或非离子表面活性剂,例如具有至多60个氧化乙烯和/或氧化丙烯单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚。通常而言,基于共聚单体的总重量,使用0.05至5重量%的保护性胶体和/或乳化剂。
为了调节分子量,可以在聚合过程中使用链转移物质。如果使用链转移剂,则基于要聚合的单体,它们通常以0.02至10.0重量%的量使用,并且分别计量加入或与反应组分预混合而计量加入。该物质的实例是卤代烷烃和卤代烯烃,例如四氯化碳、氯仿、氯甲烷、三氯乙烯、以及醛类,例如乙醛、丙醛、丁醛和异丁醛。硫醇也是合适的。优选丙醛。
所述单体可以整体计量加入,也可以初始分批加入,其余部分在已经引发聚合后再计量加入。所述计量添加可以分别进行(在空间和时间上)。聚合结束后,可以使用已知技术通过后聚合而除去残留的单体,例如通过由氧化还原催化剂引发的后聚合。挥发性残余单体也可以通过蒸馏、优选在减压下而除去,并且任选在惰性夹带气体,例如空气、氮气或蒸汽流经或通过反应器内容物的情况下而除去。
可以通过典型的方法,例如通过沉淀、过滤和随后的干燥,或者通过倾析和随后的干燥,以固态树脂的形式从水性分散体或非水溶液中分离出共聚物。干燥可以以本领域技术人员已知的方式进行,例如,在鼓式干燥器中、在流管中、在流化床中或在旋风干燥器中。
所述共聚物适合用作用于油漆和印刷油墨的粘合剂;用作用于浸渍和涂布纸、卡片、纺织品、无纺布、金属、矿物表面、木材和塑料的涂料中的粘合剂;作为生产可热封和RF可焊接膜的涂料。
应该强调的是,所述共聚物不仅溶解在常用作溶剂的酮和酯中,而且即使在室温(23℃)下无需加热也易溶于不太适合氯乙烯-乙酸乙烯酯共聚物的溶剂中,例如芳族化合物、二醇酯或二醇醚。要强调的其他性质是与极性较低的其他粘合剂的混溶性得到改善,以及对极性较低的底材的粘合性得以改善。
以下实施例用于进一步阐明本发明。
共聚物的制备:
对比实施例1:
最初在40L高压釜中加入12.5kg的水和17.5g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将1.25kg氯乙烯和0.93kg乙酸乙烯酯加入高压釜中,并将混合物搅拌30分钟。为了使液滴稳定,加入1.93kg的3.05重量%的羟丙基甲基纤维素(HPMC)的水溶液。然后将反应混合物加热至74℃的聚合温度,然后在恒定压力下开始计量加入10.3kg氯乙烯和1.3kg乙酸乙烯酯的混合物。当最终压力达到4.0巴时,终止聚合。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
对比实施例2:
最初在40L高压釜中加入15.4kg的水和16.2g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将8.24kg的氯乙烯和5.30kg的乙酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.34kg的3.05重量%的羟丙基甲基纤维素(HPMC)的水溶液。然后将反应混合物加热至71℃的聚合温度。当最终压力达到0.5巴时,终止聚合。在对悬浮液进行处理(脱气,洗涤和干燥)之后,分离出白色粉末。
发明实施例1:
最初在40L高压釜中加入15.7kg的水和38.3g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将4.25kg氯乙烯、3.54kg乙酸乙烯酯、0.7kg月桂酸乙烯酯和14.2g丙醛加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05重量%的羟丙基甲基纤维素(HPMC)的水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.7kg氯乙烯。与起始压力相比,聚合在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例2:
最初在40L高压釜中加入15.7kg的水和28.4g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将4.96kg的氯乙烯、2.13kg的乙酸乙烯酯和1.40kg的月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05重量%的羟丙基甲基纤维素(HPMC)的水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.62kg氯乙烯。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例3:
最初在40L高压釜中加入15.7kg的水和32.6g的过氧化二月桂酰。在已经使用氮气使高压釜呈惰性之后,将4.25kg的氯乙烯、2.13kg的乙酸乙烯酯和2.13kg的月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05重量%的羟丙基甲基纤维素(HPMC)的水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.6kg氯乙烯。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例4:
最初在40L高压釜中加入15.7kg的水和28.4g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将5.6kg氯乙烯、2.1kg乙酸乙烯酯和2.1kg月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05wt%的羟丙基-甲基纤维素(HPMC)水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入4.3kg氯乙烯。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例5:
最初在40L高压釜中加入15.7kg的水和32.6g的过氧化二月桂酰。在使用氮气使高压釜呈惰性之后,将4.25kg的氯乙烯、2.13kg的乙酸乙烯酯和2.13kg的月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05wt%的羟丙基-甲基纤维素(HPMC)水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.6kg氯乙烯。通过加入15g亚硝酸钠,在压力下降了3.3巴时,聚合终止。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例6:
最初在40L高压釜中加入15.7kg的水和32.6g的过氧化二月桂酰。用氮气使高压釜呈惰性后,将3.9kg氯乙烯、1.1kg乙酸乙烯酯、2.1kg月桂酸乙烯酯和14.2g丙醛加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05重量%的羟丙基-甲基纤维素(HPMC)水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入6.0kg氯乙烯和1.0kg乙酸乙烯酯的混合物。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例7:
最初在40L高压釜中加入15.7kg的水和49.6g的过氧化二月桂酰。在使用氮气使高压釜呈惰性之后,将3.54kg的氯乙烯、2.13kg的乙酸乙烯酯和2.8kg的月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05wt%的羟丙基-甲基纤维素(HPMC)水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.6kg氯乙烯。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
发明实施例8:
最初在40L高压釜中加入20.9kg的水和4.84g的过硫酸钾。用氮气使高压釜呈惰性后,将1.3kg氯乙烯、354.4g乙酸乙烯酯、708.8g月桂酸乙烯酯和6.41g二辛基磺基琥珀酸钠加入高压釜中,并将混合物搅拌20分钟。然后将反应混合物加热至70℃的聚合温度,然后在恒定压力下开始计量加入6.96kg氯乙烯、1.42kg乙酸乙烯酯、0.92kg月桂酸乙烯酯和90.90g二辛基磺基琥珀酸钠的混合物。与起始压力相比,在压力下降了1.0巴时,聚合终止。在对乳胶进行处理(脱气、沉淀、洗涤和干燥)后,分离白色粉末。
发明实施例9:
最初在40L高压釜中加入15.7kg的水、42.5g的过氧化二月桂酰和425g的马来酸。用氮气使高压釜呈惰性后,将4.25kg的氯乙烯、2.13kg的乙酸乙烯酯和2.1kg的月桂酸乙烯酯加入高压釜中,并将混合物搅拌20分钟。为了使液滴稳定,加入1.39kg的3.05重量%的羟丙基-甲基纤维素(HPMC)水溶液。然后将反应混合物加热至71℃的聚合温度,然后在恒定压力下开始计量加入5.7kg氯乙烯。与起始压力相比,在压力下降了3.5巴时,聚合结束。在对悬浮液进行处理(脱气、洗涤和干燥)之后,分离白色粉末。
测量方法:
通过1H NMR光谱确定表1中所述的聚合物组成。
K值:
K值是与聚合物的粘均摩尔质量相关的度量。使用DIN EN ISO 1628-2的方法确定K值。
玻璃化温度Tg:
使用Mettler-Toledo的DSC1动态扫描量热仪,在开放式坩埚中,以10K/min的加热速率,通过DSC(动态扫描量热法,DIN EN ISO 11357-1/2)而测定玻璃化转变温度Tg。评估为玻璃化转变温度的温度是在热流图中第二加热曲线的阶梯的中点(中点=热流动阶梯的一半阶梯高度)处的温度。
实施例中获得的共聚物概括在表1中:
表1:
性能测试:
清漆溶液的制备和溶液雾度的测定(方法A):
将120g二甲苯加入250ml玻璃瓶中,并使用高速搅拌器(溶解器)以每分钟2000转的速度在搅拌下缓慢计量加入30g待溶解的共聚物。在2000rpm下20分钟搅拌时间后,将溶液在水浴中以每分钟仅50转的搅拌加热至50℃为30分钟,然后在不搅拌的情况下使其冷却至23℃。
通过进行目视清晰度测定而评价溶解度。
视觉清晰度测定的评价量表[等级]:
1=透明溶液
2=几乎透明的溶液
3=轻微浑浊
4=浑浊
5=极其浑浊
6=不溶
表2总结了二甲苯中清晰度测定的结果。
表2:
表2表明本发明聚合物在二甲苯中的改进的溶解性,二甲苯是非极性溶剂的重要代表。
铝上涂层的密封接缝强度的测定:
类似于方法A,在每种情况下由6g三元共聚物VinnolR H 15/45M(具有84重量%VC和15重量%VA和1重量%不饱和二元羧酸的羧基官能的三元共聚物;来自Wacker ChemieAG的成膜树脂)和24g本发明实施例和对比实施例样品在120克甲乙酮中制备20重量%的溶液。
使用24μm钢丝刮刀而各自将这些溶液刮下,以在柔软的铝箔(厚度为38μm)上形成无气泡的膜。在室温下通风10分钟后,将涂覆的铝箔在干燥箱中在180℃下干燥15秒。
将涂覆的箔片在中间折叠,然后使用热接触热封机将箔片的各涂漆侧彼此密封。
密封条件:
a)时间:0.5s
b)两个密封钳口的温度(尺寸15×1厘米):180℃
c)压力:30N/cm2
从每个密封的箔上切下五个条带(每个1.5厘米宽)。借助拉伸测试设备以90°的去除角和100mm/min的速度测量密封接缝强度。平均值是由5个各自一次密封的测试而形成;结果报导为N/15mm。
在各自情况下,在将密封条在23℃的水中湿存储24小时后,确定湿密封接缝强度的值。N/15mm的值越高,密封接缝强度越好。
结果总结于表3中:
表3:
样品 | 密封接缝强度[N/15mm] | 湿密封接缝强度[N/15mm] |
对比实施例1 | 7.4 | 5.2 |
对比实施例2 | 2.5 | 1.8 |
发明实施例1 | 8.6 | 8.7 |
发明实施例2 | 10.6 | 6.7 |
发明实施例3 | 12.6 | 11.3 |
发明实施例4 | 12.9 | 12.4 |
发明实施例5 | 8.2 | 8.5 |
发明实施例6 | 11.2 | 10.8 |
发明实施例7 | 7.9 | 8.4 |
从表3中可以看出,本发明的聚合物能够增加复合材料(例如用于食品或药品包装的涂覆铝)的密封接缝强度。这也显示了一种增加涂层耐水性的方法(例如在铝上)。
Claims (9)
1.一种氯乙烯、乙酸乙烯酯与一种或多种具有3至18个碳原子的未支化或支化烷基羧酸的长链乙烯基酯的共聚物,其特征在于,其包含50-75重量%的氯乙烯单体单元,5-25重量%的乙酸乙烯酯单体单元和10-45重量%的长链乙烯基酯单体单元,重量%的数值是基于共聚单体的总重量,并且重量%的数值在每种情况下相加为100重量%。
2.如权利要求1所述的共聚物,其特征在于共聚的长链乙烯基酯包括月桂酸乙烯基酯和/或具有9至10个碳原子的α-支化的一元羧酸的乙烯基酯。
3.如权利要求1所述的共聚物,其特征在于其包含55-75重量%的氯乙烯单体单元、5-25重量%的乙酸乙烯酯单体单元和10-30重量%的月桂酸乙烯基酯单体单元。
4.如权利要求1-3之一所述的共聚物,其特征在于额外使至多10重量%的官能共聚单体共聚,其中所述官能共聚单体选自烯键式不饱和一元羧酸和二元羧酸、马来酸酐、烯键式不饱和羧酰胺和腈、烯键式不饱和磺酸和其盐、含环氧化物的共聚单体。
5.制备如权利要求1-4之一所述的共聚物的方法,其通过自由基引发聚合而制备。
6.如权利要求5所述的制备方法,其特征在于聚合在含水介质中进行。
7.如权利要求1-4之一所述的共聚物作为用于油漆和印刷油墨的粘合剂的用途。
8.如权利要求1-4之一所述的共聚物作为在用于浸渍和涂布纸、卡片、纺织品、无纺布、金属、矿物表面、木材和塑料的涂料中的粘合剂的用途。
9.如权利要求1-4之一所述的共聚物作为用于生产可热封和RF可焊接膜的涂料的用途。
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CN1756778A (zh) * | 2003-03-06 | 2006-04-05 | 瓦克聚合系统两合公司 | 环氧改性的氯乙烯-乙烯基酯共聚物固态树脂 |
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GB1199625A (en) * | 1966-10-07 | 1970-07-22 | Japanese Geon Co Ltd | Synthetic Resin Paint Composition |
DE1745563C3 (de) | 1967-09-20 | 1980-08-14 | Wacker-Chemie Gmbh, 8000 Muenchen | Verfahren zur Herstellung von wäßrigen Polymerisat-Dispersionen |
DE2206593C3 (de) | 1972-02-11 | 1980-07-03 | Wacker-Chemie Gmbh, 8000 Muenchen | Verfahren zur Herstellung von Vinylchlorid-Vinylester-Copolymerisaten |
US3836510A (en) | 1972-12-27 | 1974-09-17 | Hooker Chemical Corp | Vinyl halide terpolymer and bulk process for preparation |
DE2409800B2 (de) | 1974-03-01 | 1980-08-07 | Chemische Werke Huels Ag, 4370 Marl | Verfahren zur Herstellung carboxylgruppenhaltiger Terpolymerer mit verbesserter MetaUhaftung |
DE2822357A1 (de) * | 1978-05-23 | 1979-12-06 | Wacker Chemie Gmbh | Zusatzmittel zur herstellung von porenarmen, kunststoffhaltigen, hydraulisch abbindenden massen |
IN164548B (zh) | 1984-10-12 | 1989-04-01 | Goodrich Co B F | |
JP2502639B2 (ja) * | 1987-12-09 | 1996-05-29 | 日信化学工業株式会社 | 磁気記録媒体 |
DE3911181A1 (de) | 1989-04-06 | 1990-10-11 | Wacker Chemie Gmbh | Copolymere des vinylchlorids mit verbesserter thermischer stabilitaet und guter waermestandfestigkeit |
JP2000198821A (ja) * | 1999-01-06 | 2000-07-18 | Denki Kagaku Kogyo Kk | 塩化ビニル―酢酸ビニル系共重合体および組成物 |
JP2001049224A (ja) * | 1999-08-09 | 2001-02-20 | Sumitomo Chem Co Ltd | 接着剤組成物 |
DE10309858A1 (de) | 2003-03-06 | 2004-09-23 | Wacker Polymer Systems Gmbh & Co. Kg | Thermostabile Vinylchlorid-Mischpolymerisate |
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US3668165A (en) * | 1967-05-10 | 1972-06-06 | Wacker Chemie Gmbh | Dispersion polymerized terpolymer of vinyl acetate, vinyl ester of a fatty acid, and vinyl chloride |
CN1756778A (zh) * | 2003-03-06 | 2006-04-05 | 瓦克聚合系统两合公司 | 环氧改性的氯乙烯-乙烯基酯共聚物固态树脂 |
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