CN102378770B - 聚乙烯醇系聚合物及其制造方法 - Google Patents
聚乙烯醇系聚合物及其制造方法 Download PDFInfo
- Publication number
- CN102378770B CN102378770B CN201080015273.3A CN201080015273A CN102378770B CN 102378770 B CN102378770 B CN 102378770B CN 201080015273 A CN201080015273 A CN 201080015273A CN 102378770 B CN102378770 B CN 102378770B
- Authority
- CN
- China
- Prior art keywords
- pva
- polymerization
- general formula
- group shown
- polyvinyl alcohol
- 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
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 60
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 8
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000007127 saponification reaction Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- -1 vinyl compound Chemical class 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 25
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 229920002689 polyvinyl acetate Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 3
- 238000003929 heteronuclear multiple quantum coherence Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229940095064 tartrate Drugs 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 class 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
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical class FC(F)=C BQCIDUSAKPWEOX-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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- FVSAFCHCUDOKSI-UHFFFAOYSA-N 2-methylprop-2-enamide;propane-1-sulfonic acid Chemical compound CC(=C)C(N)=O.CCCS(O)(=O)=O FVSAFCHCUDOKSI-UHFFFAOYSA-N 0.000 description 1
- 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
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101150027068 DEGS1 gene Proteins 0.000 description 1
- YZGQDNOIGFBYKF-UHFFFAOYSA-N Ethoxyacetic acid Natural products CCOCC(O)=O YZGQDNOIGFBYKF-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LPUZTLKYAOOFDX-QXMHVHEDSA-N ethenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC=C LPUZTLKYAOOFDX-QXMHVHEDSA-N 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
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-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
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-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
- 235000021050 feed intake Nutrition 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical class FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 125000003010 ionic group Chemical group 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SEQVSYFEKVIYCP-UHFFFAOYSA-L magnesium hypophosphite Chemical compound [Mg+2].[O-]P=O.[O-]P=O SEQVSYFEKVIYCP-UHFFFAOYSA-L 0.000 description 1
- 229910001381 magnesium hypophosphite Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 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
- 150000004682 monohydrates Chemical class 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 compound 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
- 230000003287 optical effect Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 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
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 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
- 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 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- GFPSZSNVQOVZEW-UHFFFAOYSA-N sulfonylcyclohexane Chemical compound O=S(=O)=C1CCCCC1 GFPSZSNVQOVZEW-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- IZUZIVIUDTZPFE-UHFFFAOYSA-N tert-butyl decanoate Chemical compound CCCCCCCCCC(=O)OC(C)(C)C IZUZIVIUDTZPFE-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/17—Viscosity
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明提供一种聚乙烯醇系聚合物,其水溶性比现有的聚乙烯醇系聚合物优异,并且即使是部分皂化聚乙烯醇其浊点也高。本发明涉及一种聚乙烯醇系聚合物,其末端具有通式(I)所示的基团和/或其主链中具有通式(II)所示的基团。
Description
技术领域
本发明涉及新型的聚乙烯醇系聚合物及其制造方法。
背景技术
聚乙烯醇系聚合物是一种水溶性聚合物,其被广泛应用在各种产业领域中。尤其是由于聚乙烯醇系聚合物具有表面活性,因此多被用于悬浮聚合或乳液聚合的分散稳定剂、无机物或有机粉体的分散剂等。一直以来,为了进一步提高聚乙烯醇系聚合物在这些用途中的水溶性、表面活性而进行了各种尝试。例如,日本特公昭61-41924号公报中公开了在主链的一个末端具有碳数1~18的硫烷基的聚乙烯醇系聚合物,日本特开昭61-254238号公报公开了这些聚合物的表面活性优异、并且可用作水煤浆用的分散稳定剂。此外,日本特开平10-168128号公报中公开了一个末端具有离子性基团的聚乙烯醇系聚合物,并记载了其可用于乙烯基系化合物的悬浮聚合。然而,上述聚乙烯醇系聚合物虽然表面活性优异,但其水溶性尚有改善的余地。
专利文献1:日本特公昭61-41924号公报
专利文献2:日本特开昭61-254238号公报
专利文献3:日本特开平10-168128号公报。
发明内容
本发明的目的在于提供一种聚乙烯醇系聚合物,其水溶性比现有的聚乙烯醇系聚合物优异,并且即使是部分皂化聚乙烯醇其浊点也高。
达成上述目的的本发明涉及一种聚乙烯醇系聚合物,其末端具有通式(I)所示的基团和/或其主链中具有通式(II)所示的基团。
[化1]
[化2]
(式中,R表示氢原子或OM基,M表示氢原子、碱金属原子、1/2碱土金属原子或铵基。)
本发明还涉及一种改性聚乙烯醇系聚合物的制造方法,其包括:在含磷化合物的存在下使乙烯基酯系单体进行自由基聚合的工序;和对所得的聚合物进行皂化的工序。
本发明的聚乙烯醇系聚合物能够达成以下效果:其水溶性比现有的聚乙烯醇系聚合物优异,并且即使是部分皂化聚乙烯醇其浊点也高。
附图说明
图1表示由实施例1得到的PVA的1H-NMR谱图。
图2表示由实施例1得到的PVA的31P-NMR谱图。
图3表示由实施例1得到的PVA的P-H相关二维分析(HMQC)的结果。
图4表示由实施例1得到的PVA的P-H相关二维分析(HMBC)的结果。
具体实施方式
本发明的聚乙烯醇系聚合物(以下,有时简称为PVA)在末端具有通式(I)所示的基团和/或在主链中具有通式(II)所示的基团。
[化3]
[化4]
其中,R表示氢原子或OM基,M表示氢原子、碱金属原子、1/2碱土金属原子或铵基。
因此,作为本发明的PVA的形态,有在末端具有通式(I)所示的基团的PVA;在主链中具有通式(II)所示的基团的PVA;和在末端具有通式(I)所示的基团且在主链中具有通式(II)所示的基团的PVA这三种形态。
作为以M表示的碱金属原子,可列举出钠原子、钾原子等。作为以M表示的1/2碱土金属原子,可列举出1/2镁原子、1/2钙原子等。在M为1/2碱土金属原子时,剩余的1/2碱土金属原子(即2价的碱土金属原子的剩余的键合键)可与通式(I)中的氧原子、通式(II)中的氧原子、P(H2O2)等键合。
本发明的PVA的分子中含有乙烯醇单元、以及通式(I)所示的基团和/或通式(II)所示的基团,进而还可以含有源自在其制造中使用的乙烯基酯系单体的乙烯基酯系单体单元。即,本发明的PVA可以为部分皂化PVA。此外,本发明的PVA可以进一步含有能够与乙烯基酯系单体共聚的单体单元。乙烯基酯系单体以及能够与乙烯基酯系单体共聚的单体如下所述。
本发明的PVA的皂化度只要使PVA为水溶性及水分散性则没有特别的限制,皂化度优选为5摩尔%以上,更优选为7摩尔%以上,进一步优选为10摩尔%以上,皂化度的上限没有特别的限制。皂化度不到5摩尔%时,PVA的水溶性降低,可能会使制备PVA水溶液变得困难。
本发明的PVA的平均聚合度(以下,仅记载为聚合度)优选为10~3000。在聚合度超过3000时以及不足10时,该PVA的生产率降低,有可能使实用性受损。应予说明,PVA的聚合度称作粘均聚合度,例如,可根据JIS K6726进行测定。即,PVA的聚合度可如下求得:使PVA再次皂化至皂化度99.5摩尔%以上,纯化后,由在30℃的水中测得的特性粘度[η]根据下式即可求得。
P=([η]×1000/8.29)(1/0.62)
本发明的PVA的制造方法只要使所得的PVA在末端具有通式(I)所示的基团和/或在主链中具有通式(II)所示的基团,则没有特别的限制,例如,可通过包括以下工序的方法来制造:在含磷化合物的存在下使乙烯基酯系单体进行自由基聚合的工序;和对所得的聚合物进行皂化的工序。
作为乙烯基酯系单体,可列举出甲酸乙烯基酯、乙酸乙烯基酯、丙酸乙烯基酯、丁酸乙烯基酯、异丁酸乙烯基酯、特戊酸乙烯基酯、叔羧酸乙烯基酯、己酸乙烯基酯、辛酸乙烯基酯、月桂酸乙烯基酯、棕榈酸乙烯基酯、硬脂酸乙烯基酯、油酸乙烯基酯、苯甲酸乙烯基酯等,其中最优选乙酸乙烯基酯。
作为含磷化合物,可列举出次磷酸、次磷酸钠、次磷酸钾、次磷酸钙、次磷酸镁、次磷酸铵及其水合物等次磷酸化合物等,适合使用在工业上最廉价的次磷酸钠或其水合物。
含磷化合物的使用量没有特别的限制,根据欲引入PVA中的通式(I)所示的基团和通式(II)所示的基团的量进行适当设定即可。含磷化合物的使用量相对于乙烯基酯系单体100重量份优选0.001~30重量份。
乙烯基酯系单体的聚合可以在醇类溶剂等溶剂中或在无溶剂条件下进行。
作为乙烯基酯系单体的聚合中所使用的聚合方式,可以是分批聚合、半分批聚合、连续聚合、半连续聚合的任意的聚合方式。作为聚合方法,可以使用本体聚合法、溶液聚合法、悬浮聚合法、乳液聚合法等公知的任意方法。其中,适宜采用在无溶剂或醇系溶剂中进行聚合的本体聚合法或溶液聚合法,为了制造高聚合度的聚合物可采用乳液聚合法。作为醇系溶剂,可以使用甲醇、乙醇、丙醇等,但并不限于此。此外,这些溶剂也可以两种或两种以上混合使用。作为聚合中使用的引发剂,只要根据聚合方法适当选择现有公知的偶氮系引发剂、过氧化物系引发剂、氧化还原系引发剂等即可。作为偶氮系引发剂,可列举出2,2’-偶氮二异丁腈、2,2’-偶氮二(2,4-二甲基戊腈)、2,2’-偶氮二(4-甲氧基-2,4-二甲基戊腈)等,作为过氧化物系引发剂,可列举出过氧化二碳酸二异丙酯、过氧化二碳酸二-2-乙基己酯、过氧化二碳酸二乙氧基乙酯等过碳酸酯化合物;过氧化新癸酸叔丁酯、过氧化新癸酸α-枯基酯、过氧化癸酸叔丁酯等过酸酯化合物;乙酰基过氧化磺酰环已烷;2,4,4-三甲基戊基-2-过氧化苯氧基乙酸酯等。此外,也可使过硫酸钾、过硫酸铵、过氧化氢等与上述引发剂组合后作为引发剂。此外,作为氧化还原系引发剂,可列举出上述过氧化物与亚硫酸氢钠、碳酸氢钠、酒石酸、L-抗坏血酸、雕白粉等还原剂组合而成的引发剂。此外,在高温下进行乙烯基酯系单体的聚合时,由于会出现由乙烯基酯系单体的分解所致的PVA的着色等,因此,此时为了防止着色,可以在聚合体系中添加1~100ppm(相对于乙烯基酯系单体)左右的如酒石酸之类的抗氧化剂。
在乙烯基酯系单体的聚合时采用的温度优选0~200℃,更优选30~140℃。进行聚合的温度低于0℃时,无法获得充分的聚合速度,故不优选。此外,进行聚合的温度高于200℃时,难以获得目标PVA,故不优选。作为将聚合时采用的温度控制在0~200℃的方法,例如可列举出:通过控制聚合速度来使由聚合产生的发热与从反应器的表面的放热取得平衡的方法;通过使用了适当的热介质的外部夹套进行控制的方法等,从安全性方面出发,优选后者的方法。
本发明中,可以在比通常情况高的温度条件下使乙烯基酯系单体聚合而制成1,2-二醇键的含量多的PVA。此时,1,2-二醇键的含量优选1.9摩尔%以上,更优选2.0摩尔%以上,进一步优选2.1摩尔%以上。
在乙烯基酯系单体聚合时,可以在不损害本发明主旨的范围内与其他单体共聚。作为能够与乙烯基酯系单体共聚的单体,可列举出例如乙烯、丙烯、正丁烯、异丁烯等α-烯烃;丙烯酸及其盐;丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸十二烷基酯、丙烯酸十八烷基酯等丙烯酸酯类;甲基丙烯酸及其盐;甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十八烷基酯等甲基丙烯酸酯类;丙烯酰胺,N-甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、二丙酮丙烯酰胺、丙烯酰胺丙磺酸及其盐、丙烯酰胺丙基二甲基胺及其盐或其季铵盐、N-羟甲基丙烯酰胺及其衍生物等丙烯酰胺衍生物;甲基丙烯酰胺;N-甲基甲基丙烯酰胺、N-乙基甲基丙烯酰胺,甲基丙烯酰胺丙磺酸及其盐、甲基丙烯酰胺丙基二甲基胺及其盐或其季铵盐、N-羟甲基甲基丙烯酰胺及其衍生物等甲基丙烯酰胺衍生物;甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、异丙基乙烯基醚、正丁基乙烯基醚、异丁基乙烯基醚、叔丁基乙烯基醚、十二烷基乙烯基醚、硬脂基乙烯基醚等乙烯基醚类;丙烯腈、甲基丙烯腈等腈类;氯乙烯、氟乙烯等卤代乙烯类;偏二氯乙烯、偏二氟乙烯等偏卤代乙烯类;乙酸烯丙酯、烯丙基氯等烯丙基化合物;马来酸、衣康酸、富马酸等不饱和二羧酸及其盐或其酯;乙烯基三甲氧基硅烷等乙烯基甲硅烷基化合物;聚氧乙烯(甲基)丙烯酸酯、聚氧丙烯(甲基)丙烯酸酯、聚氧乙烯(甲基)丙烯酰胺、聚氧丙烯(甲基)丙烯酰胺、聚氧乙烯(1-(甲基)丙烯酰胺-1,1-二甲基丙基)酯、聚氧乙烯(甲基)烯丙基醚、聚氧丙烯(甲基)烯丙基醚、聚氧乙烯乙烯基醚、聚氧丙烯乙烯基醚等含氧化烯烃基的单体;乙酸异丙烯酯等。
此外,在乙烯基酯系单体聚合时,为了调节所得的PVA的聚合度等,还可以在不损害本发明主旨的范围内在链转移剂的存在下进行聚合。作为链转移剂,可列举出乙醛、丙醛等醛类;丙酮、甲基乙基酮等酮类;2-羟基乙硫醇、正十二烷基硫醇、3-巯基丙酸等硫醇类;四氯甲烷、一溴三氯甲烷、三氯乙烯、全氯乙烯等卤化物类。
通过在含磷化合物存在下的乙烯基酯系单体的聚合,可以获得在主链中和/或在末端加入含磷化合物的乙烯基酯(共)聚合物。
在乙烯基酯系聚合物的皂化反应中可以应用使用了现有公知的氢氧化钠、氢氧化钾、甲醇钠等碱性催化剂或对甲苯磺酸等酸性催化剂的醇解反应或水解反应。作为可在该反应中使用的溶剂,可列举出甲醇、乙醇等醇类;乙酸甲酯、乙酸乙酯等酯类;丙酮、甲基乙基酮等酮类;苯、甲苯等芳香族烃类等,这些溶剂可以单独或将两种以上组合使用。其中,以甲醇或甲醇/乙酸甲酯混合溶剂作为溶剂、以氢氧化钠用作催化剂来进行皂化反应是简便的,故优选。
根据以上的方法,可以以混合物的形式获得在末端具有通式(I)所示的基团的PVA、在主链中具有通式(II)所示的基团的PVA、以及末端具有通式(I)所示的基团且主链中具有通式(II)所示的基团的PVA。
在这样的混合物中,优选通式(I)所示的基团的改性量为0.01~18摩尔%。低于0.01摩尔%时,存在聚合度超过3000的可能性,该PVA的生产率降低,可能会使实用性受损。超过18摩尔%时,存在聚合度低于10的可能性,该PVA的生产率降低,可能会使实用性受损。应予说明,该改性量可以通过1H-NMR测定而求得。
此外,在这样的混合物中,通式(I)所示的基团与通式(II)所示的基团的摩尔比,没有特别的限制,但考虑到该PVA的生产率时,优选(通式(I))/(通式(II))=5/5~9/1。应予说明,该摩尔比可以通过31P-NMR测定而求得。
根据本发明能够提供一种聚乙烯醇系聚合物,其水溶性比现有的聚乙烯醇系聚合物优异,并且即使是部分皂化聚乙烯醇其浊点也高。
[实施例]
以下,列举实施例和比较例对本发明进行详细地说明,但本发明不受这些实施例的限制。在以下的实施例和比较例中,在无特别说明的情况下,%表示重量%。
实施例1
[PVA的制造]
向反应器中投料甲醇300g和次膦酸钠(次磷酸钠)·一水合物2.0g,制备成次膦酸钠一水合物的甲醇溶液。接着,向反应器中投料乙酸乙烯基酯1200g,通过鼓泡氮气将反应器内置换成氮气。反应器开始升温,当内温变为60℃时向反应器中添加2,2’-偶氮二异丁腈0.3g,引发聚合。在聚合中将聚合温度维持在60℃。4小时后聚合率达到50%时冷却,停止聚合。接着,在减压下除去未反应的乙酸乙烯基酯,得到聚乙酸乙烯基酯(PVAc)的甲醇溶液。向调节至40%的PVAc溶液中添加NaOH甲醇溶液(10%浓度)使碱摩尔比(NaOH的摩尔数/PVAc中的乙烯基酯单元的摩尔数)为0.03,进行皂化。通过以上操作获得皂化度98.5摩尔%的PVA。根据JIS K6726测定该PVA的粘均聚合度,为760。
将上述PVA用甲醇进行48小时的利用索氏抽提的纯化,然后溶解于d6-DMSO中,使用500MHz的1H-NMR(JEOL GX-500)进行分析。由此在δ=7.5~7.7ppm、6.3~6.6ppm处确认到在PVA的末端的来自次膦酸的质子(P-H)的质子,可以确认到在末端具有式(I)所示的基团。进而,将用上述方法纯化得到的PVA溶解于d6-DMSO,使用203MHz的31P-NMR进行分析。由此在10~13ppm和28~30ppm处可确认到两种信号(将次膦酸钠一水合物的信号设为0ppm)。进而,进行P-H相关二维分析(HMQC,HMBC),由HMQC的结果,可以确认31P-NMR的10~13ppm处的信号与1H-NMR的7.5~7.7ppm处和6.3~6.6ppm处(来自在PVA的末端存在的次膦酸的质子(P-H))的信号相关,但对于31P-NMR的28~30ppm,无法确认与直接键合的质子相关(P-H键)。由该结果可以确认不仅在末端存在改性的P而且在主链中也存在改性的P。此外,由HMBC的结果,可以确认31P-NMR的两个信号均与1H-NMR的1.1~1.9ppm处(来自PVA中的亚甲基)的信号相关。由该结果,可以确认不仅存在末端具有式(I)所示的基团的PVA而且还存在主链中具有式(II)所示的基团的PVA。
此外,由1H-NMR的分析结果,可求得通式(I)所示的基团的改性量。具体而言,由来自PVA的主链亚甲基的峰(1.1~1.9ppm)的面积α和来自通式(I)所示的基团的连接于磷的质子的峰(7.5~7.7ppm和6.3~6.6ppm)的面积β,使用下述式计算通式(I)所示的基团的改性量。
通式(I)所示的基团的改性量(摩尔%)={(峰面积β)/((峰面积α/2)+(峰面积β))}×100
进而,根据31P-NMR的分析结果,通过来自通式(I)所示的基团的磷的峰(10~13ppm)和来自通式(II)所示的基团的磷的峰(28~30ppm)的峰面积之比,计算PVA的通式(I)所示的基团与通式(II)所示的基团的摩尔比。
[浊点的测定]
一边将PVA的0.4重量%水溶液从20℃升温至70℃,一边使用UV分光光度计(岛津制作所制;UV2100)测定测定试样的光路长为1cm、波长500nm下透射率为85%时的温度,作为浊点。
实施例2
在实施例1中,改变皂化时氢氧化钠的使用量,除此以外与实施例1同样地操作,得到PVA。合成条件和评价结果如表1所示。
实施例3
在实施例1中,改变聚合时次膦酸钠一水合物、甲醇的使用量,并改变皂化时氢氧化钠的使用量,除此以外与实施例1同样地操作,得到PVA。合成条件和评价结果如表1所示。
实施例4
在实施例1中,改变聚合时次膦酸钠一水合物的使用量,并改变皂化时的PVAc浓度,除此以外与实施例1同样地操作,得到PVA。合成条件和评价结果如表1所示。
比较例1
代替次膦酸钠一水合物而使用3-巯基丙酸,在表1所示的聚合条件、皂化条件下采用与实施例1同样的方法得到了PVA。评价结果如表1所示。
比较例2
聚合时不使用次膦酸钠,在表1所示的聚合条件、皂化条件下采用与实施例1同样的方法得到PVA。评价结果如表1所示。
[表1]
产业实用性
本发明的聚乙烯醇系聚合物的水溶性比现有的聚乙烯醇系聚合物优异,并且即使是部分皂化聚乙烯醇其浊点也高,其在工业上的评价极高。
Claims (4)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009-085057 | 2009-03-31 | ||
JP2009085057 | 2009-03-31 | ||
PCT/JP2010/055446 WO2010113819A1 (ja) | 2009-03-31 | 2010-03-26 | 新規なポリビニルアルコール系重合体およびその製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102378770A CN102378770A (zh) | 2012-03-14 |
CN102378770B true CN102378770B (zh) | 2014-03-05 |
Family
ID=42828110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201080015273.3A Expired - Fee Related CN102378770B (zh) | 2009-03-31 | 2010-03-26 | 聚乙烯醇系聚合物及其制造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US8524831B2 (zh) |
EP (1) | EP2415789B1 (zh) |
JP (1) | JP5463348B2 (zh) |
KR (1) | KR101667234B1 (zh) |
CN (1) | CN102378770B (zh) |
TW (1) | TWI485162B (zh) |
WO (1) | WO2010113819A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5399351B2 (ja) * | 2010-09-07 | 2014-01-29 | 株式会社クラレ | 分散液および感熱記録材料 |
JP5615634B2 (ja) * | 2010-09-10 | 2014-10-29 | 株式会社クラレ | 水性エマルジョン |
JP5528959B2 (ja) * | 2010-09-10 | 2014-06-25 | 株式会社クラレ | 樹脂粉末 |
US10647793B2 (en) | 2014-03-28 | 2020-05-12 | Synthomer (Uk) Limited | Use of a sulphur or phosphorous-containing polymer as a processing aid in a polyvinyl chloride polymer composition |
KR102310659B1 (ko) | 2014-03-28 | 2021-10-07 | 신쏘머 (유케이) 리미티드 | 현탁중합반응을 위한 2차 현탁제 |
JP2019031581A (ja) * | 2015-12-28 | 2019-02-28 | 株式会社クラレ | 色相に優れた低重合度ビニルアルコール系重合体粉末およびその製造方法 |
BR112022018132A2 (pt) * | 2020-10-15 | 2023-04-25 | Kuraray Co | Película de resina de álcool polivinílico, método para distinguir película de resina de álcool polivinílico, e método para fabricar película de resina de álcool polivinílico |
CN114249458B (zh) * | 2021-12-21 | 2023-09-26 | 福建清源科技有限公司 | 水煤浆协同处理高浓度聚乙烯醇废水的方法及水煤浆 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101203551A (zh) * | 2005-06-16 | 2008-06-18 | 日本合成化学工业株式会社 | 水溶性膜 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58108207A (ja) | 1981-12-21 | 1983-06-28 | Kuraray Co Ltd | 新規な低重合度ポリビニルアルコ−ル系重合体 |
US4561725A (en) * | 1983-02-09 | 1985-12-31 | Canon Kabushiki Kaisha | Electro-optical device having homogeneous alignment layer hardened with cross-linking agents |
JPS6141924A (ja) | 1984-08-03 | 1986-02-28 | Mitsubishi Heavy Ind Ltd | ガスサンプラの容量測定法 |
JPH0718995B2 (ja) * | 1985-02-19 | 1995-03-06 | キヤノン株式会社 | 液晶素子 |
JPS61254238A (ja) | 1985-05-06 | 1986-11-12 | Kuraray Co Ltd | 石炭−水スラリ−用の分散安定剤 |
US4772663A (en) * | 1987-01-16 | 1988-09-20 | Air Products And Chemicals, Inc. | Copolymers of vinyl alcohol and acrylates |
EP0474885B1 (en) | 1990-04-05 | 1996-08-21 | Kuraray Co., Ltd. | Suspension polymerization of vinylic compound |
JP3150304B2 (ja) * | 1990-04-05 | 2001-03-26 | 株式会社クラレ | ポリビニルアルコール系重合体 |
JP3739195B2 (ja) | 1997-11-17 | 2006-01-25 | 積水化学工業株式会社 | ポリビニルアルコール樹脂の製造方法 |
US6046272A (en) * | 1998-01-29 | 2000-04-04 | Air Products And Chemicals, Inc. | Non yellowing, thermally stable polyvinyl alcohol |
JP2001049522A (ja) * | 1999-08-03 | 2001-02-20 | Kuraray Co Ltd | ポリビニルアルコール系難燃繊維 |
JP4930664B2 (ja) * | 2001-05-31 | 2012-05-16 | 日産化学工業株式会社 | ポリビニルアルコールを有する複合物 |
JP4383086B2 (ja) * | 2003-04-28 | 2009-12-16 | 三菱レイヨン株式会社 | 色調に優れた樹脂組成物の製造方法 |
JP2008290771A (ja) * | 2007-04-27 | 2008-12-04 | Sumitomo Chemical Co Ltd | バリア性容器の製造方法 |
US7857938B2 (en) * | 2007-04-27 | 2010-12-28 | Sumitomo Chemical Company, Limited | Method for producing a barrier container |
-
2010
- 2010-03-26 US US13/254,299 patent/US8524831B2/en active Active
- 2010-03-26 WO PCT/JP2010/055446 patent/WO2010113819A1/ja active Application Filing
- 2010-03-26 EP EP10758591.1A patent/EP2415789B1/en not_active Not-in-force
- 2010-03-26 KR KR1020117025443A patent/KR101667234B1/ko active IP Right Grant
- 2010-03-26 CN CN201080015273.3A patent/CN102378770B/zh not_active Expired - Fee Related
- 2010-03-26 JP JP2011507163A patent/JP5463348B2/ja active Active
- 2010-03-30 TW TW099109552A patent/TWI485162B/zh not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101203551A (zh) * | 2005-06-16 | 2008-06-18 | 日本合成化学工业株式会社 | 水溶性膜 |
Non-Patent Citations (4)
Title |
---|
JP特开2001-49522A 2001.02.20 |
JP特开2002-356512A 2002.12.13 |
JP特开2004-323775A 2004.11.18 |
JP特开平10-168128A 1998.06.23 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2010113819A1 (ja) | 2012-10-11 |
EP2415789B1 (en) | 2014-06-04 |
CN102378770A (zh) | 2012-03-14 |
US20110313105A1 (en) | 2011-12-22 |
KR20120015436A (ko) | 2012-02-21 |
KR101667234B1 (ko) | 2016-10-18 |
US8524831B2 (en) | 2013-09-03 |
JP5463348B2 (ja) | 2014-04-09 |
EP2415789A4 (en) | 2013-10-30 |
TWI485162B (zh) | 2015-05-21 |
TW201035115A (en) | 2010-10-01 |
EP2415789A1 (en) | 2012-02-08 |
WO2010113819A1 (ja) | 2010-10-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102378770B (zh) | 聚乙烯醇系聚合物及其制造方法 | |
CN104619730B (zh) | 悬浮聚合用分散稳定剂和乙烯基系树脂的制造方法 | |
CN111333756B (zh) | 乙烯醇系共聚物及其制造方法 | |
KR102168748B1 (ko) | 현탁 중합용 분산 안정제 및 비닐계 수지의 제조 방법 | |
ES2797701T3 (es) | Estabilizador de dispersión para la polimerización en suspensión y método de fabricación de resina de vinilo | |
JP6934469B2 (ja) | ポリビニルアルコール | |
US9505921B2 (en) | Dispersion stabilizer for suspension polymerization and vinyl resin production method | |
TW593354B (en) | Dispersion stabilizer for suspension polymerization of vinyl compound | |
CN101910214A (zh) | 乙烯醇系聚合物及含有其的膜 | |
CN104066753B (zh) | 悬浮聚合用分散稳定剂 | |
WO2019013267A1 (ja) | ポリビニルアルコール及びポリビニルアルコールの製造方法 | |
JP2009062434A (ja) | 側鎖に1,2−ジオール構造を有するポリビニルアルコール系樹脂の製造方法 | |
JP2003171423A (ja) | ポリビニルアルコール系樹脂およびその用途 | |
CN103443198A (zh) | 改性乙烯醇系聚合物溶液及其制造方法 | |
JP5730123B2 (ja) | 水性エマルション | |
KR20220029664A (ko) | 비닐알코올계 블록 공중합체 및 그 제조 방법 | |
TWI836106B (zh) | 乙烯醇系嵌段共聚物及其製造方法 | |
JP4592161B2 (ja) | 酢酸ビニル系重合体の製造法 | |
JP7488183B2 (ja) | ポリビニルアルコール系重合体及び、これを用いた成形体 | |
JP5052078B2 (ja) | ポリビニルアルコール系樹脂の製造方法 | |
JP2022120627A5 (zh) | ||
JPH09227627A (ja) | スルホン酸変性ポリビニルアルコールの製造方法 | |
CN115197344A (zh) | 聚合物制造方法,自由基聚合用组成物及自由基聚合调控剂 | |
JP2022120627A (ja) | ポリビニルエステル系重合体の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140305 |