CN101260161B - Dispersion stabilizer for suspension polymerization of vinyl compound - Google Patents
Dispersion stabilizer for suspension polymerization of vinyl compound Download PDFInfo
- Publication number
- CN101260161B CN101260161B CN2008100853225A CN200810085322A CN101260161B CN 101260161 B CN101260161 B CN 101260161B CN 2008100853225 A CN2008100853225 A CN 2008100853225A CN 200810085322 A CN200810085322 A CN 200810085322A CN 101260161 B CN101260161 B CN 101260161B
- Authority
- CN
- China
- Prior art keywords
- vinyl
- vinyl alcohol
- alcohol system
- system polymer
- polymer
- 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.)
- Expired - Fee Related
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- 239000006185 dispersion Substances 0.000 title claims abstract description 59
- 239000003381 stabilizer Substances 0.000 title claims abstract description 54
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 54
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 51
- -1 vinyl compound Chemical class 0.000 title abstract description 22
- 229920000642 polymer Polymers 0.000 claims description 172
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 133
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 36
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 24
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 229960003328 benzoyl peroxide Drugs 0.000 claims description 16
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 abstract description 40
- 238000000034 method Methods 0.000 abstract description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 8
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- 238000006116 polymerization reaction Methods 0.000 description 64
- 238000004519 manufacturing process Methods 0.000 description 39
- 238000007669 thermal treatment Methods 0.000 description 35
- 229920001567 vinyl ester resin Polymers 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 239000011118 polyvinyl acetate Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 20
- 239000003999 initiator Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 description 17
- 239000000178 monomer Substances 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012736 aqueous medium Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 8
- 229940099204 ritalin Drugs 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical class [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229920002521 macromolecule Polymers 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
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DAXJNUBSBFUTRP-RTQNCGMRSA-N (8r,9s,10r,13s,14s)-6-(hydroxymethyl)-10,13-dimethyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-dione Chemical group O=C1C=C[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC(CO)C2=C1 DAXJNUBSBFUTRP-RTQNCGMRSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
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- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical group OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-M decanoate Chemical compound CCCCCCCCCC([O-])=O GHVNFZFCNZKVNT-UHFFFAOYSA-M 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HLMAOUJZLUOWAH-UHFFFAOYSA-N ethenyl acetate 2-methylpropanoic acid Chemical compound C(=C)OC(C)=O.C(C(C)C)(=O)O HLMAOUJZLUOWAH-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
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- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound 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 1
- 229940071676 hydroxypropylcellulose Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical group CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000004800 polyvinyl chloride Substances 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
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention provides a new dispersion stabilizer that satisfies, at a high level, the performances required for a dispersion stabilizer used for suspension polymerization. A method of producing a dispersion stabilizer that is useable for suspension polymerization of a vinyl compound and contains a vinyl alcohol polymer (A) includes producing the vinyl alcohol polymer (A) by heat-treating a vinyl alcohol polymer (B) at a temperature of 90 to 180 DEG C. for 0.5 to 20 hours in an atmosphere in which an oxygen concentration is 8000 ppm or lower. The vinyl alcohol polymer (B) has a saponification degree of at least 60 mol % and contains a residual acetic acid group whose block character is in the range of 0.3 to 0.6.
Description
The application is that application number is the dividing an application for the application for a patent for invention of " dispersion stabilizer for suspension polymerization of vinyl based compound and manufacture method thereof " that 200310120326.x, the applying date be on December 11st, 2003, denomination of invention.
Technical field
The present invention relates to be used for the dispersion stabilizer and the manufacture method thereof of the suspension polymerization of vinyl based compound.
Background technology
Being manufactured on of vinyl based polymers such as vinyl chloride-based resin industrially undertaken by suspension polymerization.In this suspension polymerization, make vinyl based compounds such as disperseing vinylchlorid in the aqueous medium that contains dispersion stabilizer, use oil-soluble catalyst to carry out polymerization.Usually, factor as domination vinyl based polymer quality, can list the kind etc. of pattern, stirring velocity and the dispersion stabilizer of the kind of percent polymerization, water-monomer ratio, polymerization temperature, catalyzer and amount, polymerization tank, the influence that kind produced of dispersion stabilizer is very big among them.
The dispersion stabilizer that is used for the suspension polymerization of vinyl based compound, following item is important.[1] just obtains making the sharp-pointed function of size distribution of the vinyl based polymer particle of manufacturing with a spot of addition.[2] the vinyl based polymer particle with the manufacturing of making as far as possible evenly and porous function.This performance is easy to polymkeric substance and can prevents that the polymkeric substance of the generation of flake in the molding from being necessary for the vinyl based polymer of and handling ease big for the absorption rate that obtains softening agent, the monomeric removals such as vinylchlorid that remain in the polymer particle.[3] has the function that forms the big polymer particle of Bulk Specific Gravity.[4] have by suppressing the generation of wet foam or dry foam, suppress the function that productivity reduces.[5] the form and aspect of the vinyl based polymer of gained are not caused detrimentally affect.[6], do not make aqueous solution gonorrhoea at the polymeric when filling with substance.
In the past,, except derivatived celluloses such as methylcellulose gum, carboxymethyl cellulose, also be used alone or in combination partly-hydrolysed polyvinyl alcohol etc. as the dispersion stabilizer for suspension polymerization of vinyl based compound., existing dispersion stabilizer may not fully satisfy the performance of above-mentioned [1]-[6].
For example, as the dispersion stabilizer for suspension polymerization of vinylchlorid, the polymerization degree 2000, the polyvinyl alcohol of 80 moles of % of saponification deg and the polyvinyl alcohol (Port バ-Le, the meeting of polymer publication, 413 pages of distribution in-414 pages, 1984) of polymerization degree 700-800,70 moles of % of saponification deg are disclosed., these dispersion stabilizers have insufficient problem that satisfies the performance of above-mentioned [1]-[3].
Put down in writing the dispersion stabilizer suspension polymerization that is used for the vinyl based compound, that constitute by polyvinyl alcohol in the special fair 5-88251 communique.The mean polymerisation degree of this polyvinyl alcohol is more than 500, and the ratio Pw/Pn of weight average degree of polymerization Pw and number-average degree of polymerization Pn is below 3.0.This polyvinyl alcohol intramolecularly have carbonyl and with the vinylidene of its carbonyl adjacency.This polyvinyl alcohol, being respectively more than 0.3 and more than 0.15 under the wavelength 280nm with in the absorbancy under the wavelength 320nm in the ultraviolet absorption spectrum of 0.1% aqueous solution, is more than 0.30 in the absorbancy (b) of wavelength 320nm with respect to the ratio (b)/(a) in the absorbancy (a) of wavelength 280nm.
Put down in writing the dispersion stabilizer suspension polymerization that is used for vinylchlorid, that constitute by polyvinyl alcohol in the Te Kaiping 5-105702 communique.This polyvinyl alcohol, saponification deg are 75-85 mole %, and the absorbancy under wavelength 280nm of the 0.1 weight % aqueous solution is more than 0.1, and the content of carboxyl is 0.01-0.15 mole %, and the cloud point of the 0.1 weight % aqueous solution is more than 50 ℃., these 2 kinds of stablizers that are made of polyvinyl alcohol also have the shortcoming of the performance that may not satisfy above-mentioned [1]-[5].
Te Kaiping 8-208724 communique discloses the dispersion agent of the monomeric suspension polymerization that is used to have the ethene unsaturated double-bond, and this dispersion agent is made of vinyl alcohol system polymer.This vinyl alcohol system polymer, the absorbancy under wavelength 280nm of the 1 weight % aqueous solution is more than 2.5, mean polymerisation degree is more than 500, saponification deg is 60-90 mole %, weight-average molecular weight Mw is below 2.5 with respect to the ratio Mw/Mn of number-average molecular weight Mn, the block characteristic relevant with saponification deg (Block ロ Star Network キ ヤ ラ Network タ one) is below 0.45, and the composition that dissolves in methyl alcohol is below the 10 weight %.This dispersion agent demonstrates the obtainable performance of comparison equilibrated to the requirement of above-mentioned [1]-[3], but the situation of the performance that the requirement to above-mentioned [6] is not being met is arranged.
Summary of the invention
The objective of the invention is to, under such situation, provide the novel dispersion stabilizer that satisfies the desired performance of dispersion stabilizer that suspension polymerization uses with high level.The inventor has finished following invention for solving the result that above-mentioned problem is studied repeatedly with keen determination.
Manufacture method of the present invention is the manufacture method of dispersion stabilizer that contains vinyl alcohol system polymer (A) and be used for the suspension polymerization of vinyl based compound, it contains following operation: with saponification deg is that 60 moles more than the %, the block characteristic of remaining acetoxyl are the vinyl alcohol system polymer (B) of 0.3-0.6 scope, in the atmosphere below oxygen concn 8000ppm under 90-180 ℃ of temperature thermal treatment 0.5-20 hour, thus the operation of above-mentioned vinyl alcohol system polymer (A) made.
Dispersion stabilizer of the present invention is the dispersion stabilizer that contains vinyl alcohol system polymer (A ') and be used for the suspension polymerization of vinyl based compound, the 0.1 weight % aqueous solution of above-mentioned vinyl alcohol system polymer (A ') is more than 0.7 at the ratio (b)/(a) of absorbancy under the wavelength 280nm (a) and the absorbancy under wavelength 320nm (b), the above-mentioned aqueous solution is more than 80% 30 ℃ the transmissivity at wavelength 500nm, and the YI of the 1 weight % aqueous solution of above-mentioned vinyl alcohol system polymer (A ') is below 40.
The dispersion stabilizer that obtains by the present invention, with existing dispersion stabilizer ratio, owing to obtained to be attached to effects such as the polymer scale of polymerization tank inwall is few, so the dispersion stabilizer of the application of the invention can stably carry out suspension polymerization.By using this dispersion stabilizer, can suppress to result from the foaming of vinyl alcohol system polymer, and, by using this dispersion stabilizer suspension polymerization ethylene base system compound, can make the high polymer particle of Bulk Specific Gravity.This polymer particle, gel voltinism and plasticizer absorption height, excellent in workability is therefore industrial extremely useful.
Embodiment
Embodiment of the present invention below are described.The present invention relates to contain the dispersion stabilizer and the manufacture method thereof of vinyl alcohol system polymer (below be sometimes referred to as vinyl alcohol system polymer (A)).Dispersion stabilizer of the present invention only otherwise run counter to and the invention is intended to also can contain vinyl alcohol system polymer (A) key element in addition.Dispersion stabilizer of the present invention can be used as the stablizer of the suspension polymerization of vinyl based compound.
Manufacture method of the present invention contains following operation: with saponification deg is that 60 moles more than the %, the block characteristic of remaining acetoxyl are the vinyl alcohol system polymer of 0.3-0.6 scope (below be sometimes referred to as vinyl alcohol system polymer (B)) under the atmosphere below the oxygen concn 8000ppm, under 90-180 ℃ of temperature thermal treatment 0.5-20 hour, makes the operation of vinyl alcohol system polymer (A) thus.In addition, the dispersion stabilizer that contains the vinyl alcohol system polymer (A) that useful this manufacture method makes has constituted another side of the present invention.
In preferred 1 example of the present invention, between the vinyl alcohol system polymer (A) after vinyl alcohol system polymer before thermal treatment (B) and the thermal treatment, the difference of the block characteristic of remaining acetoxyl is more than 0.02, and the difference of the surface tension of the 0.4 weight % aqueous solution is below the 0.5mN/m.
In preferred 1 example of the present invention, between the vinyl alcohol system polymer (A) after vinyl alcohol system polymer before thermal treatment (B) and the thermal treatment, the difference of 4 weight % viscosity in aqueous solution is below the 0.5mPas.
The block characteristic of the remaining acetoxyl of the vinyl alcohol system polymer (B) before the thermal treatment is 0.3-0.6, preferred 0.32-0.58, further preferred 0.35-0.55.In this specification sheets,, mean when the vinyl ester based polymer being carried out saponification manufacturing vinyl alcohol system polymer, not by the saponified acetoxyl as remaining acetoxyl.The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer (B) is lower than 0.3 occasion, and the operability of the aqueous solution of the vinyl alcohol system polymer after the thermal treatment (A) worsens.The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer (B) surpasses 0.6 occasion, the plasticizer absorption reduction of the ethylene-based polymer that obtains by the suspension polymerization of having used vinyl alcohol system polymer (A).At this,,, be described in detail its measuring method etc. in 10,532 (1977) at Port バ-Le (meeting of polymer publication, issued in 1984, the 246th page-249 pages) and Macromolecules about the block characteristic of remaining acetoxyl.
Simple declaration block characteristic.Block characteristic η represents with following formula.
η＝(OH，OAc)/[2·(OH)(OAc)]
Wherein, (OH) and (OAc) represent the mole fraction of vinyl alcohol units and the mole fraction of vinyl acetate unit respectively.(OH, the mole fraction of the structure that OAc) expression vinyl alcohol units and vinyl acetate unit is continuous.The occasion of vinyl alcohol units and the complete alternately configured of vinyl acetate unit, (OH, OAc)=1, (OH)=(OAc)=0.5, it is η=2 as a result.The occasion of vinyl alcohol units and the random configuration of vinyl acetate unit, η=1.The occasion of vinyl alcohol units and the complete blockization of vinyl acetate unit, η=0.The ratio that is the more big blockization of η is more little.
The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer can be adjusted by employed saponification catalyzer and solvent types etc. when vinyl alcohol system polymer is made in the saponification of vinyl ester based polymer.Compare the vinyl alcohol system polymer that the sour saponification of use acidic cpd can obtain having high block characteristic usually in the saponification catalyzer with in the saponification catalyzer, using the alkali soapization of basic cpd.
The oxygen concn of the atmosphere of vinyl alcohol system polymer (B) when heat-treating is below the 8000ppm, preferably below the 5000ppm, is more preferably below the 2000ppm.Oxygen concn surpasses the occasion of 8000ppm, vinyl alcohol system polymer after the thermal treatment is painted, cause detrimentally affect for the form and aspect of the vinyl based polymer that obtains by the suspension polymerization of having used the vinyl alcohol system polymer after the thermal treatment, simultaneously, the plasticizer absorption reduction of the vinyl based polymer that obtains by the suspension polymerization of having used the vinyl alcohol system polymer after the thermal treatment.In addition, the oxygen concn of the atmosphere when heat-treating is preferably more than the 5ppm, more preferably more than the 10ppm, is preferably more than the 20ppm especially.Atmosphere when heat-treating contains in temperature below 180 ℃ and the nonreactive basically gas formation of vinyl alcohol system polymer when removing deoxidation.As such gas, can list into the rare gas of argon or helium representative and nitrogen etc., in industrial preferred nitrogen.
Temperature during the thermal treatment of vinyl alcohol system polymer (B) is 90-180 ℃, is preferably 95-170 ℃, more preferably 100-160 ℃.In the occasion of thermal treatment temp less than 90 ℃, the effect that can not obtain fully sometimes producing (for example the stability during suspension polymerization improves) by thermal treatment.When thermal treatment temp surpasses 180 ℃, crosslinked by the thermal treatment vinyl alcohol system polymer sometimes.Its result, the nonsoluble that becomes the reason of flake in the vinyl based polymer that obtains by the suspension polymerization of having used vinyl alcohol system polymer (A) becomes many.
The heat treatment time of vinyl alcohol system polymer (B) is 0.5-20 hour, is preferably 1-18 hour, more preferably 1-16 hour.Heat treatment time is less than 0.5 hour occasion, the operability step-down of the aqueous solution of vinyl alcohol system polymer.In the successive production process, from the viewpoint of the quality of the vinyl alcohol system polymer (A) paying attention to obtaining after the thermal treatment, heat treatment time surpasses 5 hours more preferably.Heat treatment time surpasses 20 hours occasion, the plasticizer absorption reduction of the vinyl based polymer that is obtained by the suspension polymerization of having used vinyl alcohol system polymer (A).
The vinyl alcohol system polymer (B) before the thermal treatment and the saponification deg of the vinyl alcohol system polymer (A) after the thermal treatment all are 60 moles more than the %, are preferably more than the 65-95 mole %, more preferably 68-90 mole %.The saponification deg of vinyl alcohol system polymer is less than the occasion of 60 moles of %, the water-soluble reduction of vinyl alcohol system polymer, and operability worsens.
The vinyl alcohol system polymer (B) before the thermal treatment and the sodium acetate content of the vinyl alcohol system polymer (A) after the thermal treatment are preferably below the 3.0 weight %.The lower limit of Dichlorodiphenyl Acetate sodium content is not particularly limited, but is preferably more than the 0.01 weight %.
Between the vinyl alcohol system polymer (A) after vinyl alcohol system polymer before thermal treatment (B) and the thermal treatment, the difference of the block characteristic of remaining acetoxyl is preferably more than 0.02, more preferably more than 0.025, more preferably more than 0.03.The difference of the block characteristic of remaining acetoxyl is less than 0.02 occasion, and the stability during suspension polymerization that thermal treatment sometimes brings improves effect and do not demonstrate fully.
Between the vinyl alcohol system polymer (A) after vinyl alcohol system polymer before thermal treatment (B) and the thermal treatment, the difference of the surface tension of its 0.4 weight % aqueous solution is preferably below the 0.5mN/m, more preferably below the 0.45mN/m, more preferably below the 0.4mN/m.0.4 the difference of the surface tension of the weight % aqueous solution surpasses the occasion of 0.5mN/m, sometimes the plasticizer absorption reduction of the vinyl based polymer that is obtained by the suspension polymerization of having used vinyl alcohol system polymer (A).
Between the vinyl alcohol system polymer (A) after vinyl alcohol system polymer before thermal treatment (B) and the thermal treatment, the difference of its 4 weight % viscosity in aqueous solution is preferably below the 0.5mPas, more preferably below the 0.45mPas, more preferably below the 0.4mPas.The difference of 4 weight % viscosity in aqueous solution surpasses the occasion of 0.5mPas, sometimes the plasticizer absorption reduction of the vinyl based polymer that is obtained by the suspension polymerization of having used vinyl alcohol system polymer (A).
Vinyl alcohol system polymer (A) and mean polymerisation degree (B) all are preferably 500-4000, and more preferably 600-3500 further is preferably 650-3000.The mean polymerisation degree of vinyl alcohol system polymer is less than 500 occasion, and polymerization stability reduces when suspension polymerization ethylene base system compound.The mean polymerisation degree of vinyl alcohol system polymer is greater than 4000 occasion, and the operability of vinyl alcohol system polymer reduces or its productivity reduces sometimes.
The manufacture method of vinyl alcohol system polymer (B) is not particularly limited, and is monomer and the vinyl ester based polymer saponified method that obtains but usually use the polymerization of vinyl ester.As vinyl ester is known method such as monomeric polymerization process, applicable solution polymerization process, mass polymerization, suspension polymerization, emulsion polymerization.
As being used for vinyl ester is monomeric polymeric polymerization starter, suits to select known azo series initiators, superoxide series initiators, redox series initiators etc. according to polymerization process.As the azo series initiators, for example can use 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile) etc.As the superoxide series initiators, for example can use peroxocarbonate compounds such as diisopropyl peroxydicarbonate, two-2-ethylhexyl peroxy dicarbonate and diethoxy ethyl peroxy dicarbonate; Over-churning compounds such as tert-butyl hydroperoxide neodecanoic acid ester, α-cumyl new decanoate ester peroxide and tert-butyl hydroperoxide decylate; Acetyl cyclohexyl sulphonyl superoxide and 2,4,4-tri-methyl-amyl-2-peroxidation phenylium ester etc.Have, the material that has made up Potassium Persulphate, ammonium persulphate or hydrogen peroxide etc. also can be used in above-mentioned initiator as initiator again.As the redox series initiators, can list the material that reductive agents such as sodium bisulfite, sodium bicarbonate, tartrate, L-xitix and rongalite and above-mentioned superoxide are combined.In addition, polymerization temperature is selected from 0-180 ℃ scope usually.
As vinyl ester is monomer, can list vinyl formate, vinyl acetate, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, trimethylacetic acid vinyl acetate, its storehouse acid of Barcelona (バ one サ チ Star Network acid) vinyl acetate, vinyl caproate, sad vinyl acetate, vinyl laurate, palmitinic acid vinyl acetate, stearic acid vinyl ester, oleic acid vinyl acetate and vinyl benzoate etc.Among them, vinyl acetate most preferably.Use the occasion of vinyl acetate separately, the polymerization vinyl acetate is made polyvinyl acetate (PVA), by this polyvinyl acetate (PVA) of saponification, can access vinyl alcohol system polymer (B).Vinyl alcohol system polymer (B) also can be substantially free of ethylene unit.At this, what is called is substantially free of ethylene unit and means that the containing ratio of ethylene unit is less than 0.5 mole of %.
When vinyl ester is monomer polymerization, the scope of not damaging purport of the present invention also can copolymerization other monomer.As the monomer of copolymerization, for example also can use alpha-olefins such as ethene, propylene, n-butene, iso-butylene.Also can use vinylformic acid and salt thereof.In addition, also can use esters of acrylic acids such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-EHA, dodecylacrylate, vinylformic acid stearyl.In addition, also can use methacrylic acid and salt thereof.In addition, also can use methyl acrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate, methacrylic acid 2-ethylhexyl, lauryl methacrylate, methacrylic acid stearyl.In addition, also can use acrylamide.In addition, also can use N methacrylamide, N-ethyl acrylamide, N,N-DMAA, diacetone acrylamide, acrylamide propanesulfonic acid and salt, acrylamide propyl-dimethyl amine and salt thereof or acrylamide derivatives such as its quaternary salt, N hydroxymethyl acrylamide and derivative thereof.In addition, also can use Methacrylamide.In addition, also can use N-methyl acrylamide, N-ethyl-methyl acrylamide, Methacrylamide propanesulfonic acid and salt, dimethylaminopropyl methacrylamide and salt thereof or methacrylamide derivatives such as its quaternary salt, N-methylol methacrylamide and derivative thereof.In addition, also can use methylvinylether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ether vinyl ethers such as (ス テ ア リ Le PVC ニ Le エ one テ Le).In addition, also can use nitriles such as vinyl cyanide, methacrylonitrile.In addition, also can use ethylene halide classes such as vinylchlorid, vinyl fluoride.In addition, also can use vinylidene chloride, vinylidene isogonic ethylene halide class.In addition, also can use allylic cpds such as allyl acetate, chlorallylene.In addition, also can use unsaturated dicarboxylic acid and salt or its esters such as toxilic acid, furoate clothing, fumaric acid.In addition, also can use vinyl silyl compounds such as vinyltrimethoxy silane.In addition, also can use isopropenyl acetate.In addition, also can be used in combination these monomers are a plurality of.
When vinyl ester is monomer polymerization, be purpose with the polymerization degree of regulating resulting vinyl ester based polymer etc., carrying out vinyl ester in the presence of chain-transfer agent is that monomeric polymerization is also passable.As chain-transfer agent, can list aldehydes such as acetaldehyde, propionic aldehyde, butyraldehyde, phenyl aldehyde; Ketones such as acetone, methyl ethyl ketone, hexanone, pimelinketone; Thio-alcohols such as 2-hydroxyl sulfur alcohol, lauryl mercaptan; Halogenated hydrocarbon such as trieline, tetrachloroethylene.Among them, preferably use aldehydes and ketone.The addition of chain-transfer agent is determined according to the chain transfer constant of the chain-transfer agent that adds and the polymerization degree of target vinyl ester based polymer, usually, wishes with respect to vinyl ester to be that monomer is 0.1-10 weight %.
The saponification of vinyl ester based polymer can enough known method carry out, for example applicable used an acidic catalysts such as basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate and tosic acid, alcoholysis reaction or hydrolysis reaction.Can use alcohols such as methyl alcohol, ethanol as solvent; Ester such as ritalin, vinyl acetic monomer class; Ketone such as acetone, methyl ethyl ketone; Benzene, toluene etc. are aromatic hydrocarbon based etc.These solvents can separately or make up more than 2 kinds and use.Wherein, be solvent with methyl alcohol or methyl alcohol/ritalin mixed solvent, and with sodium hydroxide be used for catalyzer saponification reaction its implement easily.
Make a preferred example of the method for vinyl alcohol system polymer (B), at first intramolecularly have the compound (for example aldehydes and ketone etc.) of carbonyl and initiator in the presence of, the polymerization of vinyl ester is a monomer, manufacturing vinyl ester based polymer.Then, by being carried out saponification, resulting vinyl ester based polymer makes vinyl alcohol system polymer.
Secondly, the dispersion stabilizer of the present invention of the suspension polymerization that is used for the vinyl based compound is described.This dispersion stabilizer is made of vinyl alcohol system polymer (below be sometimes referred to as vinyl alcohol system polymer (A ')).This vinyl alcohol system polymer (A ') available the invention described above method manufacturing.Moreover dispersion stabilizer of the present invention only otherwise violate the intent of the present invention also can contain vinyl alcohol system polymer (A ') key element in addition.
Vinyl alcohol system polymer (A ') below is described.The 0.1 weight % aqueous solution of vinyl alcohol system polymer (A ') is more than 0.7 in the absorbancy (a) of wavelength 280nm with at the ratio (b)/(a) of the absorbancy (b) of wavelength 320nm.In addition, the 0.1 weight % aqueous solution of vinyl alcohol system polymer (A ') is more than 80% 30 ℃ the transmissivity at wavelength 500nm.In addition, the YI of the 1 weight % aqueous solution of vinyl alcohol system polymer (A ') is below 40.
The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer (A ') is preferably more than 0.35.In addition, in vinyl alcohol system polymer (A '), the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn is preferably the scope of 2.1-4.9.
The 0.1 weight % aqueous solution of vinyl alcohol system polymer (A ') is preferably more than 0.1 in the absorbancy (a) of wavelength 280nm, more preferably more than 0.2, further is preferably more than 0.25.The upper limit of absorbancy (a) is not particularly limited, and for example is below 0.8.In addition, the above-mentioned aqueous solution is preferably more than 0.07 in the absorbancy (b) of wavelength 320nm, more preferably more than 0.09, further is preferably more than 0.1.The upper limit of absorbancy (b) is not particularly limited, and for example is below 0.6.Absorbancy (b) is more than 0.7 with the ratio (b)/(a) of absorbancy (a), is preferably 0.7-1.5.(b)/(a) less than 0.7 occasion, the polymerization stability of vinyl based compound when suspension polymerization becomes bad sometimes.Moreover above-mentioned absorbancy can be measured with the method for explanation in an embodiment.
The ratio (b)/(a) of above-mentioned absorbancy is adjusted to method more than 0.7, can lists with acid or the method for alkaline purification vinyl alcohol system polymer, the method for thermal treatment vinyl alcohol system polymer etc.
The YI of the 1 weight % aqueous solution of vinyl alcohol system polymer (A ') is below 40, is preferably below 35, more preferably below 30.The YI of the 1 weight % aqueous solution of vinyl alcohol system polymer (A ') surpasses 40 occasion, and when the polymkeric substance that processing is obtained by suspension polymerization, polymkeric substance is painted, and is therefore not preferred.YI (yellow Index, yellowness index) is the value of expression yellow chromaticity, from colourless or whitely be shown as and be positive amount according to the table of degree of form and aspect apart from the jaundice direction.The YI value is more little, approaches colourless or white more.
The 0.1 weight % aqueous solution of vinyl alcohol system polymer (A ') is more than 80% 30 ℃ the transmissivity at wavelength 500nm, is preferably more than 82%, more preferably more than 85%.Less than 80% occasion, the operability of the aqueous solution of vinyl alcohol system polymer worsens the 0.1 weight % aqueous solution of vinyl alcohol system polymer 30 ℃ transmissivity.
The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer (A ') is preferably more than 0.35, more preferably more than 0.37, further is preferably more than 0.4.The block characteristic of the remaining acetoxyl of vinyl alcohol system polymer is lower than 0.35 occasion, and the operability of the aqueous solution of vinyl alcohol system polymer worsens sometimes.
The weight-average molecular weight Mw of vinyl alcohol system polymer (A ') is 2.1-4.9 with respect to the ratio Mw/Mn of number-average molecular weight Mn, and more preferably 2.2-4.7 further is preferably 2.2-4.4.The Mw/Mn value is greater than 4.9 occasion, and the size distribution of the vinyl based polymer particle that the suspension polymerization by the vinyl based compound obtains broadens.Moreover the number-average molecular weight Mn of vinyl alcohol system polymer and weight-average molecular weight Mw are the values of measuring with the gel permeation chromatography of narrating later (GPC).
The Mw/Mn of above-mentioned vinyl alcohol system polymer can be with various method adjustment, for example available following method adjustment.The 1st is the method for the different vinyl alcohol system polymer of the fusion polymerization degree.The 2nd be with fusion the material saponified method of the different vinyl ester based polymer of the polymerization degree.The 3rd is to use polymerization degree conditioning agents such as aldehydes, halogenated hydrocarbon, thio-alcohol, makes the vinyl ester based polymer that contains the low polymerization degree composition, and the method for the resulting vinyl ester based polymer of saponification.The 4th is that to carry out vinyl ester with multi-stage type be monomeric polyreaction, regulates polymerization degree in its each stage, makes the vinyl ester based polymer, and the method for the resulting vinyl ester based polymer of saponification.The 5th is that the adjustment vinyl ester is the percent polymerization of monomeric polyreaction, makes the vinyl ester based polymer, and the method for the resulting vinyl ester based polymer of saponification.
The saponification deg of vinyl alcohol system polymer (A ') is preferably 60 moles more than the %, more preferably more than the 65-95 mole %, further is preferably 68-90 mole %.The saponification deg of vinyl alcohol system polymer has the water-soluble reduction of vinyl alcohol system polymer less than the occasion of 60 moles of %, the situation that operability worsens.
The mean polymerisation degree of vinyl alcohol system polymer (A ') is preferably 500-4000, and more preferably 600-3500 further is preferably 650-3000.The mean polymerisation degree of vinyl alcohol system polymer is less than 500 occasion, and polymerization stability reduces when suspension polymerization ethylene base system compound.The mean polymerisation degree of vinyl alcohol system polymer is greater than 4000 occasion, the plasticizer absorption reduction of the vinyl based polymer that the suspension polymerization by the vinyl based compound sometimes obtains, and perhaps the size-grade distribution of vinyl based polymer particle broadens.
Below, illustrate that the suspension polymerization of the vinyl based compound by having used dispersion stabilizer of the present invention makes an example of the method for vinyl based polymer.
Use dispersion stabilizer of the present invention in aqueous medium during suspension polymerization ethylene base system compound, the temperature of aqueous medium is not particularly limited, even for example 20 ℃-90 ℃ scope or also all can use well more than it.This aqueous medium can be made of pure water, perhaps can be made of the aqueous solution that contains various added ingredientss or the aqueous medium that contains other organic solvents.Supplying with the amount of the aqueous medium of polyreaction system, can be the fully amount of heated polymerizable reaction system of energy.In addition, in order to improve except that thermo-efficiency, the polymerizer that has reflux exchanger also can use well.
In the occasion of using dispersion stabilizer of the present invention to carry out the suspension polymerization of vinyl based compound, consumption about dispersion stabilizer is not particularly limited, be preferably the 0.01-5 weight part with respect to vinyl based compound 100 weight parts, more preferably the 0.02-2 weight part further is preferably the 0.02-1 weight part.
Dispersion stabilizer of the present invention also can use individually, but in aqueous medium during suspension polymerization ethylene base system compound, also can and with normally used other dispersion stabilizers.As such dispersion stabilizer, for example can use the water-soluble cellulose ether of methylcellulose gum, hydroxy ethyl cellulose, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE etc.In addition, also can use water-soluble polymerss such as vinyl alcohol system polymer, gelatin.In addition, also can use oil-soluble emulsifiers such as Span-20, sorbitan trioleate, tristearin, ethylene oxide-propylene oxide block copolymer.In addition, also can use water soluble emulsifiers such as Tween-20, polyoxyethylene oleic acid glyceride, sodium laurate etc.About and the addition of the dispersion agent of usefulness be not particularly limited, but per 100 parts by weight of ethylene base system compounds are preferably the 0.01-1.0 weight part.
In the suspension polymerization of the vinyl based compound that has used dispersion stabilizer of the present invention, be used for the polymeric material of vinyl based compound since can using over as polymerization starter.Specifically can use and at above-mentioned vinyl ester be the same initiator of material that exemplifies in the monomeric polymerization.
In addition, in the suspension polymerization of the vinyl based compound that has used dispersion stabilizer of the present invention, the various additives that polymerization system added as required other are also passable.As additive, for example can list polymerization retarders such as polymerization regulators such as aldehydes, halogenated hydrocarbon, thio-alcohol, phenolic compound, sulphur compound, N-oxide compound etc.In addition, also can at random add pH and adjust agent, scale inhibitor, linking agent etc., also can be also with a plurality of above-mentioned additives.
As the vinyl based compound that can use dispersion stabilizer suspension polymerization of the present invention, for example can list single vinylchlorid and based on the monomer mixture (more than the vinylchlorid 50 weight %) of vinylchlorid.As with the comonomer (comonomer) of chloroethylene copolymer, for example can use vinyl ester such as vinyl acetate, propionate; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate; Alpha-olefin such as ethene, propylene; Unsaturated dicarboxylic acid such as maleic anhydride, furoate clothing class; Vinyl cyanide, vinylbenzene, vinylidene chloride, vinyl ether, other and vinylchlorid can copolymerization monomer.And, even independent polymerization or the copolymerization occasion of the above-mentioned vinyl compound of vinyl-chloride-containing not also can be used dispersion stabilizer of the present invention.
For the suspension polymerization of the vinyl based compound that has used dispersion stabilizer of the present invention, the condition that foundations such as the charging ratio of each composition, polymerization temperature are always adopted in the suspension polymerization of vinyl based compounds such as vinylchlorid is determined to get final product.In addition, has no restriction about vinyl based compound, polymerization starter, aqueous medium and other conditions (for example loading sequence of additive and ratio).In addition, when using warm water as aqueous medium, the method for heating vinyl based compound is also used well before the vinyl based compound is encased in polymerizer.
As explained above, according to the present invention, can obtain obtaining being attached to effects such as the polymer scale of polymerization tank inwall is few and can stablize the dispersion stabilizer that carries out suspension polymerization.By using this dispersion stabilizer, can suppress to result from the foaming of vinyl alcohol system polymer.In addition, by using this dispersion stabilizer suspension polymerization ethylene base system compound, can make plasticizer absorption and Bulk Specific Gravity height, painted few vinyl based polymer particle.
[embodiment]
Below enumerate embodiment and be described in more detail the present invention, but the present invention is not limited to these embodiment fully.Moreover in following embodiment, only otherwise special declaration, " % " means " weight % ".
(analysis of vinyl alcohol system polymer)
The analytical procedure of vinyl alcohol system polymer below is described.
(1) mean polymerisation degree
Mean polymerisation degree is measured according to the method JISK6726 of regulation in Japanese Industrial Standard (JIS).
(2) saponification deg
Saponification deg is measured according to JIS K6726.
(3) block characteristic
The block characteristic is according to Port バ-Le (meeting of polymer publication, distribution in 1984, the 246th page-249 pages) and Macromolecules, the measuring method of putting down in writing in 10,532 (1977), from
13The peak in the methylene radical zone of C-NMR is obtained.More particularly, carry out
13The mensuration of C-NMR is by " CHOH-CH
2-CHOH-" pairing absorption intensity of methylene radical and " CHOH-CH in the structure
2-CHOAc-" pairing absorption intensity of methylene radical and " CHOAc-CH in the structure
2-CHOAc-" the pairing absorption intensity of methylene radical in the structure, calculate above-mentioned mole fraction (OH), (OAc) and (OH, OAc).Then by mole fraction (OH), (OAc) and (OH OAc) determines the block characteristic.
(4) surface tension
The 0.4 weight % aqueous solution of modulation vinyl alcohol system polymer uses tensiometer (the consonance length of schooling of coming to the surface; CBUP-A3), adopt the Wilhelmy method to measure its surface tension at 20 ℃.
(5) viscosity
Viscosity is measured according to JIS K6726.
(6) absorbancy
Modulated the 0.1 weight % aqueous solution of vinyl alcohol system polymer as measuring test portion.Measure test portion for this, under optical length 1cm, be determined at wavelength 280nm and in the absorbancy of 320nm.Mensuration has been used UV spectrophotometer (Shimadzu Seisakusho Ltd.'s system; UV2100).
(7)YI
Modulated the 1 weight % aqueous solution of vinol series polymer, measured its YI according to JIS K7103.Mensuration has been used colour-difference meter (Japanese electric look system; ZE-200).
(8) transmissivity
For the 0.1 weight % aqueous solution (30 ℃) of vinyl alcohol system polymer, measured the transmissivity of test portion under the optical length 1cm, the time at wavelength 500nm.Mensuration has been used UV spectrophotometer (Shimadzu Seisakusho Ltd.'s system; UV2100).
(9) calculating of Mw/Mn
With single dispersion poly-methyl methacrylate base ester is standard specimen, and the hexafluoroisopropanol that will contain sodium trifluoroacetate 20 micromoles per liter is used for mobile phase, carries out GPC at 40 ℃ and measures, and obtains the weight-average molecular weight Mw and the number-average molecular weight Mn of vinyl alcohol system polymer.Then, calculate Mw/Mn by the measured value that obtains.
(evaluating characteristics of monomeric polymerizability of vinyl chloride and resulting vinyl chloride-based polymer)
The below evaluation of the characteristic of explanation monomeric polymerizability of vinyl chloride and resulting vinyl chloride-based polymer.
(10) median size
The dry screen assay determination size-grade distribution of the wire netting by having used the Tyler mesh benchmark is obtained median size.
(11) Bulk Specific Gravity
Bulk Specific Gravity is measured according to JIS K6721.
(12) plasticizer absorption (CPA)
Adopt the method for putting down in writing among the ASTM-D3367-75 to measure the absorbed dose of the phtalic acid dioctyl ester in the time of 23 ℃.
(13) foaminess
The chloroethylene polymerization that detects by an unaided eye begins the interior foamed state of reactor after 30 minutes, according to following benchmark evaluation.At this, liquid level is the height from reactor bottom surface 70%.
AA: can't see foaming substantially.
A: the height from the reactor bottom surface to 75-80% can be seen bubble.
B: the height from the reactor bottom surface to 80-90% can be seen bubble.
C: the height from the reactor bottom surface to 90-100% can be seen bubble.
(14) polymerization stability
After being fetched into polymer slurries outside the reactor, the attachment state of the dirt (scale) in the visual inspection reactor is with adhering to of following benchmark evaluation dirt.
A: almost do not have adhering to of polymer scale.
B: the polymer scale that can confirm white at reactor wall.
C: the polymer scale that can confirm white at reactor wall morely.
(15) tint permanence of vinyl chloride-base polymer
Mix vinyl chloride-base polymer 100 weight parts, toxilic acid dibutyl tin 2.5 weight parts and as phtalic acid dioctyl ester 40 weight parts of softening agent, with 170 ℃ open type roller mixing 5 minutes, obtain the sheet material of the about 1mm of thickness.The detect by an unaided eye coloring degree of this sheet material is followingly judged like that.
A: non-coloring almost.
B: painted a little.
C: considerably painted.
(Production Example 1 of vinyl alcohol system polymer)
The Production Example of vinyl alcohol system polymer below is described.After at first being encased in vinyl acetate 133kg, methyl alcohol 7.0kg, acetaldehyde 2.7kg in the reactor, frothing and to use nitrogen replacement in the reactor by nitrogen.Therewith dividually, with 2,2 '-azobis isobutyronitrile is dissolved in methyl alcohol, and the initiator solution of modulation concentration 0.8g/L carries out the nitrogen displacement with this initiator solution by frothing of nitrogen.
Secondly, the intensification of beginning reactor when internal temperature reaches 60 ℃, is added above-mentioned initiator solution 420mL in reactor, begin polymerization thus.Keeping polymerization temperature in the polymerization is 60 ℃, with 1310mL/ hour ratio continuously add above-mentioned initiator solution on one side, implement polymerization on one side.Begin 4 hours postcooling containers in polymerization and stop polymerization.This percent polymerization constantly is 40%.Then, Yi Bian under 30 ℃ decompression, add methyl alcohol often,, obtain the methanol solution (concentration: 50%) of polyvinyl acetate (PVA) Yi Bian remove unreacted Vinyl Acetate Monomer from reaction soln.
From then on the methanol solution of polyvinyl acetate (PVA) is gathered a part, add the methanol solution of the sodium hydroxide of concentration 10%, make alkali mol ratio (alkali cpd is with respect to the unitary mol ratio of the vinyl acetate in the polyvinyl acetate (PVA)) reach 0.5, placed 5 hours at 60 ℃, carry out saponification (saponification).After saponification ends, implement to utilize tired special the extraction 3 days of Suo Kesi of methyl alcohol, then, carried out drying under reduced pressure 3 days, obtain the purified polyvinyl alcohol at 80 ℃.Measure the mean polymerisation degree of this polyvinyl alcohol according to JIS K6726, the result is 700.
Add the methanol solution of the sodium hydroxide of water, methyl alcohol, ritalin and concentration 10% to the methanol solution of the polyvinyl acetate (PVA) of above-mentioned concentration 50%, make and reach polyvinyl acetate (PVA) 30%, water 1%, ritalin 30% and alkali mol ratio 0.018 are carried out the saponification of polyvinyl acetate (PVA).Generation gelation in about 3 minutes after adding alkali.With pulverizer pulverize this gelation material, placed 1 hour at 40 ℃, carry out saponification.Thereafter, the mixing solutions of ritalin/water=8/2 is joined in the reaction system with the amount identical with the solution of reaction system, remaining alkali neutralizes.After using phenolphthalein indicator to confirm that neutralization is over, obtain polyvinyl alcohol with centrifugal dewatering.After 1 day, measure its saponification deg at this polyvinyl alcohol of 60 ℃ of dryings according to JIS K6726.Saponification deg is 70 moles of %.Under the nitrogen atmosphere of oxygen concn 400ppm, this polyvinyl alcohol was heat-treated 10 hours, obtain vinyl alcohol system polymer (P-1) at 120 ℃.
(the Production Example 2-16 of vinyl alcohol system polymer)
The Intake Quantity of Vinyl Acetate Monomer, methyl alcohol, initiator and acetaldehyde during the polymerization of appropriate change Vinyl Acetate Monomer; Alkali mol ratio and solvent composition during the saponification reaction of polyvinyl acetate (PVA); And oxygen concn, the temperature and time of the atmosphere the during thermal treatment of vinyl alcohol system polymer, in addition, similarly make vinyl alcohol system polymer (P-2 to P-16) with Production Example 1.
(Production Example 17 of vinyl alcohol system polymer)
In Production Example 17, be that material has been made vinyl alcohol system polymer with 2 kinds of polyvinyl acetate (PVA).Particularly, at first be encased in vinyl acetate 133kg, methyl alcohol 7.0kg, acetaldehyde 5.8kg in the reactor after, froth and will use nitrogen replacement in the reactor by nitrogen.Therewith dividually, with 2,2 '-azobis isobutyronitrile is dissolved in methyl alcohol, and the initiator solution of modulation concentration 0.8g/L carries out the nitrogen displacement with this initiator solution by frothing of nitrogen.
Secondly, the intensification of beginning reactor when internal temperature reaches 60 ℃, is added above-mentioned initiator solution 420mL in reactor, begin polymerization thus.Keeping polymerization temperature in the polymerization is 60 ℃, with 1310mL/ hour ratio continuously add above-mentioned initiator solution on one side, implement polymerization on one side.Begin 4.5 hours postcooling containers in polymerization and stop polymerization.This percent polymerization constantly is 40%.Then, Yi Bian under 30 ℃ decompression, add methyl alcohol often,, obtain the methanol solution (concentration: 60%) of polyvinyl acetate (PVA) Yi Bian remove unreacted Vinyl Acetate Monomer from reaction soln.
From then on the methanol solution of polyvinyl acetate (PVA) is gathered a part, add the methanol solution of the sodium hydroxide of concentration 10%, make alkali mol ratio (alkali cpd is with respect to the unitary mol ratio of the vinyl acetate in the polyvinyl acetate (PVA)) reach 0.5, placed 5 hours, make it to carry out saponification at 60 ℃.After saponification ends, implement to use tired special the extraction 3 days of Suo Kesi of methyl alcohol, then, carried out drying under reduced pressure 3 days, obtain the purified polyvinyl alcohol at 80 ℃.Measuring the result of the mean polymerisation degree of this polyvinyl alcohol according to JIS K6726, is 450.
In addition, change the Intake Quantity of Vinyl Acetate Monomer, methyl alcohol, initiator, acetaldehyde, similarly carry out polymerization with above-mentioned in addition, obtain the polyvinyl acetate (PVA) of mean polymerisation degree 1000.
The polyvinyl acetate (PVA) of the mean polymerisation degree 450 that obtains like this with weight ratio 55/45 fusion and the polyvinyl acetate (PVA) of mean polymerisation degree 1000 obtain the polyvinyl acetate (PVA) of mean polymerisation degree 700.This polyvinyl acetate (PVA) is dissolved in methyl alcohol, the methanol solution of the polyvinyl acetate (PVA) of modulation concentration 55%.Then, add the methanol solution of the sodium hydroxide of water, methyl alcohol, ritalin and concentration 10%, make to reach polyvinyl acetate (PVA) 30%, water 1%, ritalin 30% and alkali mol ratio 0.02, carry out the saponification of polyvinyl acetate (PVA) to this methanol solution.Generation gelation in about 5 minutes after adding alkali.With pulverizer pulverize this gelation material, placed 1 hour at 40 ℃, make it to carry out saponification.Thereafter, the mixing solutions of ritalin/water=8/2 is joined in the reaction system with the amount identical with the solution of reaction system, remaining alkali neutralizes.After using phenolphthalein indicator to confirm that neutralization is over, utilize centrifugal dewatering to obtain vinyl alcohol system polymer.In drying machine, at this vinyl alcohol system polymer of 60 ℃ of dryings, after 1 day, under nitrogen atmosphere, heat-treated 10 hours, obtain vinyl alcohol system polymer (P-17) at 120 ℃.
More than the P-1 to P-17 that obtains create conditions and thermal treatment before and after the analytical results of vinyl alcohol polymer be shown in table 1 and table 2.Moreover Production Example 14 and 15 is the Production Examples of not heat-treating, the block characteristic difference of both acetoxyls.In addition, the evaluation result of table 2 is to have deducted the evaluation result of the vinyl alcohol system polymer after the thermal treatment of P-14 and P-15.In table 2, the evaluation result of P-14 and P-15 is the evaluation result of the vinyl alcohol system polymer before the thermal treatment.
[table 1]
The symbol * of table 1 represents to be separated and can not measure.
[table 2]
| ? | Title | The polymerization degree | Saponification deg mole % | Absorbancy under 280nm (a) | Absorbancy under 320nm (b) | (b)/(a) | YI | Transmission % | Block characteristic after the thermal treatment | Mw/Mn |
| Production Example 1 | P-1 | 700 | 70 | 0.274 | 0.313 | 1.14 | 10.2 | 97.5 | 0.523 | 2.1 |
| Production Example 2 | P-2 | 1700 | 78 | 0.020 | 0.030 | 1.50 | 11.1 | 98.9 | 0.513 | 2.2 |
| Production Example 3 | P-3 | 2300 | 85 | 0.011 | 0.013 | 1.18 | 12.2 | 99.3 | 0.549 | 2.1 |
| Production Example 4 | P-4 | 700 | 70 | 0.453 | 0.060 | 0.13 | 7.1 | 82.5 | 0.395 | 2.1 |
| Production Example 5 | P-5 | 700 | 70 | 0.243 | 0.350 | 1.44 | 20.5 | 98.7 | 0.562 | 2.1 |
| Production Example 6 | P-6 | 700 | 70 | 0.277 | 0.305 | 1.10 | 16.4 | 95.3 | 0.501 | 2.2 |
| Production Example 7 | P-7 | 700 | 70 | 0.300 | 0.301 | 1.00 | 25.3 | 94.5 | 0.462 | 2.2 |
| Production Example 8 | P-8 | 700 | 70 | 0.335 | 0.277 | 0.83 | 38.6 | 94.0 | 0.435 | 2.4 |
| Production Example 9 | P-9 | 1700 | 78 | 0.032 | 0.019 | 0.59 | 35.3 | 94.2 | 0.529 | 2.2 |
| Production Example 10 | P-10 | 700 | 70 | 0.453 | 0.070 | 0.15 | 8.2 | 72.1 | 0.400 | 2.1 |
| Production Example 11 | P-11 | 700 | 70 | 0.256 | 0.363 | 1.41 | 45.1 | 99.2 | 0.540 | 2.1 |
| Production Example 12 | P-12 | 700 | 70 | 0.357 | 0.227 | 0.66 | 50.2 | 93.2 | 0.420 | 2.5 |
| Production Example 13 | P-13 | 700 | 70 | 0.412 | 0.216 | 0.52 | 61.8 | 92.0 | 0.410 | 2.7 |
| Production Example 14 | P-14 | 2300 | 85 | 0.021 | 0.001 | 0.05 | 8.2 | 93.2 | 0.502 | 2.1 |
| Production Example 15 | P-15 | 2300 | 85 | 0.020 | 0.001 | 0.05 | 8.3 | 93.2 | 0.544 | 2.1 |
| Production Example 16 | P-16 | 1700 | 50 | 0.028 | 0.023 | 1.46 | 12.5 | 53.2 | 0.511 | 2.2 |
| Production Example 17 | P-17 | 700 | 72 | 0.315 | 0.319 | 1.01 | 9.4 | 97.0 | 0.500 | 2.2 |
By table 1 and table 2 as can be known, by thermal treatment, variation has taken place in the block characteristic of vinyl alcohol system polymer.In above-mentioned example, when heat-treating under oxygen concn 5ppm-8000ppm, 100 ℃-140 ℃ of temperature, 5 hours-18 hours condition of heat treatment time, the value of block characteristic increases widely.By under the atmosphere of the certain scope of oxygen concn, heat-treating in this wise, can obtain at the good vinyl alcohol system polymer of surface tension, the viscosity of the occasion of making the aqueous solution, obtain painted less, the effect of operability excellence.
(the polymerization of vinylchlorid; Embodiment 1-9 and comparative example 1-8)
Use above-mentioned vinyl alcohol system polymer (P-1 to P-17) as dispersion stabilizer, carried out the suspension polymerization of vinylchlorid.
At first, in the autoclave of lass lining system, pack into deionized water 40 weight parts that dissolved dispersion stabilizer (P-1 to P-17), 70% toluene solution, 0.04 weight part of diisopropyl peroxydicarbonate.Secondly, the degassing in the autoclave is reached 0.0067MPa, remove deoxidation.Thereafter, vinyl chloride monomer 30 weight parts of packing in autoclave under agitation are warmed up to reaction soln 57 ℃ and carry out polymerization.When polymerization began, the pressure in the autoclave was 0.83MPa, and polymerization becomes 0.44MPa after beginning 7 hours.Stop polymerization quarter at this moment, remove unreacted vinyl chloride monomer, take out content, dehydrate.The polymerization recovery rate of vinyl chloride-base polymer is 85%, and mean polymerisation degree is 1050.With estimate the polymerizability of vinylchlorid, resulting vinyl chloride-base polymer characteristic the results are shown in table 3.
[table 3]
As shown in Table 3, the vinyl alcohol system polymer by using P-1 to P-8 and P-17 can stably be made the good polyvinyl chloride of characteristic as dispersion stabilizer.
More than enumerate example embodiment of the present invention have been described, but the invention is not restricted to above-mentioned embodiment,, also can be suitable for for other embodiment based on technological thought of the present invention.
Claims (1)
1. the dispersion stabilizer for suspension polymerization of vinyl based compound, this dispersion stabilizer contains vinyl alcohol system polymer, can be used in the suspension polymerization of vinyl based compound, the 0.1 weight % aqueous solution of described vinyl alcohol system polymer is more than 0.7 at the ratio b/a of the absorbancy b under the wavelength 320nm and absorbancy a under wavelength 280nm, the described aqueous solution is at 30 ℃, transmissivity under the wavelength 500nm is more than 80%, the yellowness index YI of the 1 weight % aqueous solution of described vinyl alcohol system polymer is below 40, above-mentioned absorbancy a, above-mentioned absorbancy b and above-mentioned transmissivity are measured with optical length 1cm, the block characteristic η of the remaining acetoxyl of wherein said vinyl alcohol system polymer is more than 0.35, and the weight-average molecular weight Mw of described vinyl alcohol system polymer and the ratio Mw/Mn of number-average molecular weight Mn are 2.1-4.9
Described block characteristic η represents with following formula,
η＝(OH，OAc)/[2·(OH)(OAc)]，
Wherein, (OH) and (OAc) represent the mole fraction of vinyl alcohol units and the mole fraction of vinyl acetate unit respectively, (OH, the mole fraction of the structure that OAc) expression vinyl alcohol units and vinyl acetate unit are continuous,
The mensuration of described block characteristic η is: carry out
13The mensuration of C-NMR, by-CHOH-CH
2The pairing absorption intensity of methylene radical in the-CHOH-structure and-CHOH-CH
2The pairing absorption intensity of methylene radical in the-CHOAc-structure and-CHOAc-CH
2The pairing absorption intensity of methylene radical in the-CHOAc-structure, calculate above-mentioned mole fraction (OH), (OAc) and (OH, OAc), then by described mole fraction (OH), (OAc) and (OH OAc) calculates described block characteristic η according to following formula.
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| JP359606/2002 | 2002-12-11 | ||
| JP2002359606A JP2004189889A (en) | 2002-12-11 | 2002-12-11 | Dispersion stabilizer for suspension polymerization of vinyl compound |
| JP359605/2002 | 2002-12-11 | ||
| JP2002359605A JP3995584B2 (en) | 2002-12-11 | 2002-12-11 | Method for producing dispersion stabilizer for suspension polymerization of vinyl compounds |
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| WO2008015739A1 (en) | 2006-08-01 | 2008-02-07 | The Nippon Synthetic Chemical Industry Co., Ltd. | Dispersion stabilizer for vinyl compound suspension polymerization |
| DE102007033970A1 (en) * | 2007-07-19 | 2009-01-22 | Kuraray Europe Gmbh | Use of tempered polyvinyl alcohols as stabilizer additive of PVC |
| WO2015019613A1 (en) * | 2013-08-07 | 2015-02-12 | 株式会社クラレ | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin |
| GB201405624D0 (en) * | 2014-03-28 | 2014-05-14 | Synthomer Uk Ltd | Method of making a branched polymer, a branched polymer and uses of such a polymer |
| JP6446869B2 (en) * | 2014-07-14 | 2019-01-09 | 株式会社クラレ | Ethylene-modified polyvinyl alcohol and aqueous emulsion |
| JP6446870B2 (en) * | 2014-07-14 | 2019-01-09 | 株式会社クラレ | Polyvinyl alcohol and aqueous emulsion |
| WO2016009631A1 (en) * | 2014-07-14 | 2016-01-21 | 株式会社クラレ | Polyvinyl alcohol, and aqueous emulsion, adhesive, and emulsion polymerization dispersant comprising same |
| JP6981258B2 (en) * | 2016-12-21 | 2021-12-15 | 三菱ケミカル株式会社 | Polyvinyl alcohol resin, dispersant and dispersant for suspension polymerization |
| SG11202003752UA (en) * | 2018-02-08 | 2020-05-28 | Denka Company Ltd | Modified vinyl alcohol-based polymer and dispersion stabilizer for suspension polymerization |
| WO2020138341A1 (en) * | 2018-12-27 | 2020-07-02 | 積水化学工業株式会社 | Vinyl alcohol polymer and method for producing vinyl alcohol polymer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107860A (en) * | 1993-05-07 | 1995-09-06 | 信越化学工业株式会社 | Process for preparing vinyl chloride polymer of quality |
| US5780547A (en) * | 1991-08-06 | 1998-07-14 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Dispersing stabilizer for suspension polymerization of vinyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780547A (en) * | 1991-08-06 | 1998-07-14 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Dispersing stabilizer for suspension polymerization of vinyl chloride |
| CN1107860A (en) * | 1993-05-07 | 1995-09-06 | 信越化学工业株式会社 | Process for preparing vinyl chloride polymer of quality |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平5-105702A 1993.04.27 |
| JP特开平8-208724A 1996.08.13 |
| JP特开平8-283313A 1996.10.29 |
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| JP3995584B2 (en) | 2007-10-24 |
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