JP2010121116A - Method for producing vinyl chloride polymer - Google Patents
Method for producing vinyl chloride polymer Download PDFInfo
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- JP2010121116A JP2010121116A JP2009238504A JP2009238504A JP2010121116A JP 2010121116 A JP2010121116 A JP 2010121116A JP 2009238504 A JP2009238504 A JP 2009238504A JP 2009238504 A JP2009238504 A JP 2009238504A JP 2010121116 A JP2010121116 A JP 2010121116A
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- Prior art keywords
- vinyl chloride
- vanadium
- ligand
- chloride polymer
- group
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 53
- -1 aluminum compound Chemical class 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 7
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000008282 halocarbons Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000004581 coalescence Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000005292 vacuum distillation Methods 0.000 description 11
- IDIDIJSLBFQEKY-UHFFFAOYSA-N ethanol;oxovanadium Chemical compound [V]=O.CCO.CCO.CCO IDIDIJSLBFQEKY-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZVNVZZFUDFWRRL-UHFFFAOYSA-K O(C1=CC=CC=C1)[Ti](C1(C(=C(C(=C1C)C)C)C)C)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound O(C1=CC=CC=C1)[Ti](C1(C(=C(C(=C1C)C)C)C)C)(OC1=CC=CC=C1)OC1=CC=CC=C1 ZVNVZZFUDFWRRL-UHFFFAOYSA-K 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940057995 liquid paraffin Drugs 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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 238000000746 purification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
本発明は、特定のバナジウム化合物及び特定のアルミニウム化合物を用い、熱安定性に優れた塩化ビニル系重合体を生産性良く製造できる新規な製造方法に関するものである。 The present invention relates to a novel production method capable of producing a vinyl chloride polymer excellent in thermal stability with high productivity using a specific vanadium compound and a specific aluminum compound.
従来、塩化ビニル系重合体は一般的にラジカル重合開始剤を用いた懸濁重合法により製造されており、安価で優れた物理的、機械的性質を有した熱可塑性プラスチックとして多方面の分野で幅広く使用されている。しかしながら、上記のような一般的な方法により得られる塩化ビニル系重合体は頭−頭結合や分岐構造などの異常構造を含んでおり、それらの要因が得られる塩化ビニル系重合体の熱安定性を著しく低下させている。 Conventionally, a vinyl chloride polymer is generally produced by a suspension polymerization method using a radical polymerization initiator, and is inexpensive and has excellent physical and mechanical properties as a thermoplastic plastic in various fields. Widely used. However, the vinyl chloride polymer obtained by the general method as described above contains an abnormal structure such as a head-to-head bond or a branched structure, and the thermal stability of the vinyl chloride polymer from which these factors are obtained. Is significantly reduced.
上記欠点を解消するために、例えば、ハーフチタノセン化合物を用いた重合法が提案されている(非特許文献1)。しかし、該重合法で得られた塩化ビニル系重合体は、一般的なラジカル重合で得られる塩化ビニル系重合体よりも熱安定性は向上しているが、重合速度、触媒活性ならびに収率が低く、生産性が良好とはいえない。また、この重合系にはバナジウム化合物に比べて高価なメチルアルミノキサンを多く用いる必要があり経済的に不利である。 In order to eliminate the above disadvantages, for example, a polymerization method using a half titanocene compound has been proposed (Non-patent Document 1). However, the vinyl chloride polymer obtained by the polymerization method has improved thermal stability than the vinyl chloride polymer obtained by general radical polymerization, but the polymerization rate, catalytic activity and yield are high. Low and productivity is not good. In addition, this polymerization system is economically disadvantageous because it requires more expensive methylaluminoxane than vanadium compounds.
本発明は、上記従来技術の問題に鑑みてなされたものであり、生産性を犠牲にすることなく熱安定性に優れた塩化ビニル系重合体を製造することができる方法を提供することを課題とする。 The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a method capable of producing a vinyl chloride polymer having excellent thermal stability without sacrificing productivity. And
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、特定のバナジウム化合物及び特定のアルミニウム化合物を用いることにより、熱安定性に優れた塩化ビニル系重合体を生産性良く製造することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have produced a vinyl chloride polymer excellent in thermal stability with high productivity by using a specific vanadium compound and a specific aluminum compound. As a result, the present invention has been completed.
すなわち、一般式Vi(=O)jZk
(式中、iはバナジウム原子の酸化数を示し、2〜5の整数である。jは0又は1である。Zは配位子であり、ヘテロ原子でバナジウムと結合することができる有機配位子、ハロゲン配位子、置換されていてもよい単環式炭化水素配位子、又は置換されていてもよい多環式炭化水素配位子を示し、複数のZは同一でも異なっていてもよく、二以上のZが結合して該式中のバナジウム原子も構成員として環を形成していてもよい。kは配位子の数を示し、1〜5の整数である。)
で示される少なくとも一種類のバナジウム化合物(A)及び少なくとも一種類のアルミニウム化合物(B)の存在下で、塩化ビニル系単量体の重合反応を行うことを特徴とする塩化ビニル系重合体の製造方法を提供する。
That is, the general formula V i (= O) j Z k
(Wherein i represents the oxidation number of the vanadium atom and is an integer of 2 to 5. j is 0 or 1. Z is a ligand, and an organic compound capable of binding to vanadium at a hetero atom. A ligand, a halogen ligand, an optionally substituted monocyclic hydrocarbon ligand, or an optionally substituted polycyclic hydrocarbon ligand, wherein a plurality of Z are the same or different Or two or more Z's may combine to form a ring with the vanadium atom in the formula as a member.k represents the number of ligands and is an integer of 1 to 5.)
Production of a vinyl chloride polymer, wherein a vinyl chloride monomer is polymerized in the presence of at least one vanadium compound (A) and at least one aluminum compound (B). Provide a method.
本発明の製造方法によれば、極めて熱安定性に優れる塩化ビニル系重合体を効率的に生産することができることからその工業的価値は非常に高いものである。しかも、この方法によれば、アルミノキサンの使用量が従来技術に比して著しく少ない。 According to the production method of the present invention, a vinyl chloride polymer having extremely excellent thermal stability can be efficiently produced, so that its industrial value is very high. Moreover, according to this method, the amount of aluminoxane used is significantly less than that of the prior art.
・バナジウム化合物:
本発明に用いられるバナジウム化合物は上記一般式(1)で表されるバナジウム化合物である。該化合物は1種単独でも2種以上組合わせて使用してもよい。
・ Vanadium compounds:
The vanadium compound used in the present invention is a vanadium compound represented by the general formula (1). These compounds may be used alone or in combination of two or more.
一般式(1)における配位子Zで表されるヘテロ原子でバナジウムと結合することができる有機配位子において、ヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。ヘテロ原子でバナジウムと結合することができる有機配位子としては、例えばメトキシ配位子、エトキシ配位子、n−プロポキシ配位子、イソプロポキシ配位子、n−ブトキシ配位子、イソブトキシ配位子等のアルコキシ配位子、フェノキシ配位子、ナフトキシ配位子等のアリーロキシ配位子、アセチルアセトン配位子、カルボキシレート配位子、サリチルアルドイミン配位子、サレン配位子、ポルフィリン配位子等が挙げられ、これらは置換されていてもよい。これらの中でも、好ましくはアルコキシ配位子、アリーロキシ配位子、サリチルアルドイミン配位子、サレン配位子が好ましく、これらは置換されていてもよい。 In the organic ligand that can be bonded to vanadium by the hetero atom represented by the ligand Z in the general formula (1), examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of organic ligands that can be bonded to vanadium through a heteroatom include methoxy ligands, ethoxy ligands, n-propoxy ligands, isopropoxy ligands, n-butoxy ligands, isobutoxy ligands. Alkoxy ligands such as ligands, aryloxy ligands such as phenoxy ligands and naphthoxy ligands, acetylacetone ligands, carboxylate ligands, salicylaldoimine ligands, salen ligands, porphyrins A ligand etc. are mentioned, These may be substituted. Among these, an alkoxy ligand, an aryloxy ligand, a salicylaldoimine ligand, and a salen ligand are preferable, and these may be substituted.
また、一般式(1)における配位子Zで表されるハロゲン配位子としては、例えばフッ素配位子、塩素配位子、臭素配位子等が挙げられる。 Moreover, as a halogen ligand represented by the ligand Z in General formula (1), a fluorine ligand, a chlorine ligand, a bromine ligand etc. are mentioned, for example.
さらに、一般式(1)における配位子Zで表される置換されてもよい単環式炭化水素配位子又は多環式炭化水素配位子としては、例えば、シクロペンタジエニル配位子、インデニル配位子、フルオレニル配位子が挙げられる。触媒活性を高められる点で、kは4または5が好ましい。 Furthermore, examples of the monocyclic hydrocarbon ligand or polycyclic hydrocarbon ligand which may be substituted represented by the ligand Z in the general formula (1) include, for example, a cyclopentadienyl ligand. , Indenyl ligand, and fluorenyl ligand. In view of enhancing the catalytic activity, k is preferably 4 or 5.
ここで、触媒活性とはバナジウム化合物の触媒としての活性を意味し、単位時間当たりにバナジウム化合物1モルから生成する塩化ビニル系重合体の質量として定義される。 Here, the catalytic activity means the activity of the vanadium compound as a catalyst, and is defined as the mass of the vinyl chloride polymer produced from 1 mol of the vanadium compound per unit time.
上記バナジウム化合物の中では、例えばバナジウム(V)オキシトリエトキシド等のバナジウム(V)オキシトリアルコキシド、バナジウム(V)オキシサレン及びバナジウム(IV)オキシサレンが好ましく、それらは置換されていてもよい。 Among the vanadium compounds, vanadium (V) oxytrialkoxide such as vanadium (V) oxytriethoxide, vanadium (V) oxysalen, and vanadium (IV) oxysalen are preferable, and they may be substituted.
本発明における有機バナジウム化合物の重合系内における濃度についてはとくに限定されないが、バナジウム金属濃度で0.01〜100mmol/L、好ましくは1〜10mmol/Lの範囲である。この濃度が低すぎると収率が低下する傾向がある。また、高すぎると重合活性や重合速度、重合収率の増大効果が飽和し、生産性が良いとはいえない。 The concentration of the organic vanadium compound in the polymerization system in the present invention is not particularly limited, but the vanadium metal concentration is 0.01 to 100 mmol / L, preferably 1 to 10 mmol / L. If this concentration is too low, the yield tends to decrease. On the other hand, if it is too high, the effect of increasing the polymerization activity, polymerization rate and polymerization yield is saturated, and it cannot be said that the productivity is good.
・アルミニウム化合物:
本発明におけるアルミニウム化合物は、好ましくは、一般式AlX3(式中、Xは独立にハロゲン原子、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアルコキシ基又は置換されていてもよいアリーロキシ基を示す。)で表されるアルミニウム化合物、一般式{−Al(R1)O−}p(式中、R1は独立に置換されていてもよいアルキル基を示す。pは1以上の整数を表す。)で示される構造を有する環状のアルミノキサン、及び一般式R2{−Al(R2)O−}qAlR2 2(式中、R2は独立に置換されていてもよいアルキル基を示す。qは1以上の整数を表す。)で示される構造を有する線状のアルミノキサンから成る群から選択される少なくとも1種のアルミニウム化合物である。
Aluminum compound:
The aluminum compound in the present invention is preferably represented by the general formula AlX 3 (wherein X is independently a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy). Group or an aryloxy group which may be substituted.), An aluminum compound represented by the general formula {-Al (R 1 ) O—} p (wherein R 1 is an alkyl which may be independently substituted) A cyclic aluminoxane having a structure represented by the general formula R 2 {—Al (R 2 ) O—} q AlR 2 2 (wherein R 2 represents An alkyl group which may be independently substituted, q represents an integer of 1 or more) at least one aluminization selected from the group consisting of linear aluminoxanes having the structure Thing is.
ここで、一般式AlX3で示されるアルミニウム化合物の具体例としては、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム等のトリアルキルアルミニウムが挙げられる。 Here, specific examples of the aluminum compound represented by the general formula AlX 3 include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.
次に、一般式{−Al(R1)O−}pで示される構造を有する環状のアルミノキサン及び一般式R2{−Al(R2)O−}qAlR2 2で示される構造を有する線状のアルミノキサンにおけるR1及びR2の具体例としては、メチル、エチル、n−プロピル、イソプロピル、n−ブチル、イソブチル、n−ペンチル、ネオペンチル等のアルキル基を例示することができる。p及びqは1以上の整数、好ましくは1〜40の整数である。より好ましくは、R1及びR2はメチル、エチル、プロピル、イソブチルであり、p及びqは3〜20の整数である。但し、アルミノキサンはその主鎖を構成するAl−O−Al結合の切断と形成が比較的起こり易いため、時間の経過とともに又は熱を受けて、環状構造が線状構造に、あるいは線状構造が環状構造に変化し易く、また、上記式中のp及びqも変化し易い。したがって、アルミノキサンは、通常、様々の鎖長の、環状構造のものと線状構造のものとの混合物の状態で存在し、構造を明確に特定することは困難である。 Then, having the general formula {-Al (R 1) O-} cyclic aluminoxane having the structure represented by p and the general formula R 2 {-Al (R 2) O-} structure represented by q AlR 2 2 Specific examples of R 1 and R 2 in the linear aluminoxane include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and neopentyl. p and q are integers of 1 or more, preferably 1 to 40. More preferably, R 1 and R 2 are methyl, ethyl, propyl, isobutyl, and p and q are integers of 3-20. However, since aluminoxane is relatively easy to cut and form the Al—O—Al bond constituting the main chain, the cyclic structure becomes a linear structure or the linear structure is changed with the passage of time or heat. It is easy to change to a cyclic structure, and p and q in the above formula are also likely to change. Accordingly, aluminoxane usually exists in a mixture of a cyclic structure and a linear structure having various chain lengths, and it is difficult to clearly identify the structure.
上記アルミノキサンの中で、R1又はR2がメチルであるメチルアルミノキサンが特に好ましい。該メチルアルミノキサンは、通常、環状構造のメチルアルミノキサン及び線状構造のメチルアルミノキサンの混合物である。 Among the aluminoxanes, methylaluminoxane, in which R 1 or R 2 is methyl, is particularly preferable. The methylaluminoxane is usually a mixture of a methylaluminoxane having a cyclic structure and a methylaluminoxane having a linear structure.
また、上記アルミニウム化合物の濃度としては、触媒活性を考慮すると、上記有機バナジウム化合物のバナジウム原子とのモル比において、アルミニウム原子/バナジウム原子のモル比が0.1〜100、好ましくは0.5〜10の範囲である。このモル比が小さすぎても大きすぎても収率と触媒活性が低下する傾向がある。 Moreover, as the concentration of the aluminum compound, considering the catalytic activity, the molar ratio of the aluminum atom / vanadium atom is 0.1-100, preferably 0.5- The range is 10. If this molar ratio is too small or too large, the yield and catalytic activity tend to decrease.
本発明の製造方法は、塊状重合法、溶液重合法等の一般的な重合様式で行うことができる。そして、溶液重合を行う際の溶媒としては特に制限はなく、慣用的な溶媒、例えば、n−ペンタン、n−ヘキサン、n−ヘプタン、n−オクタン、n−イソオクタン、シクロヘキサン、メチルシクロヘキサン等のアルカン又はシクロアルカン、トルエン、キシレン、エチルベンゼン、モノ又はジアルキルナフタレン等のアルキル芳香族炭化水素、クロロメタン、塩化メチレン、クロロホルム、四塩化炭素、1,2−ジクロロエタン、クロロベンゼン、クロロナフタレン、オルトジクロロベンゼン等のハロゲン化炭化水素、テトラヒドロナフタレン、デカヒドロナフタレン等の水素化芳香族炭化水素、高分子量液状パラフィン又はそれらの混合物を挙げることができ、中でもハロゲン化炭化水素が収率と触媒効率を高められる点で好ましい。 The production method of the present invention can be carried out by a general polymerization method such as a bulk polymerization method or a solution polymerization method. And there is no restriction | limiting in particular as a solvent at the time of performing solution polymerization, For example, alkanes, such as n-pentane, n-hexane, n-heptane, n-octane, n-isooctane, cyclohexane, methylcyclohexane, etc. Or alkyl aromatic hydrocarbons such as cycloalkane, toluene, xylene, ethylbenzene, mono- or dialkylnaphthalene, chloromethane, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, chloronaphthalene, orthodichlorobenzene, etc. Examples include halogenated hydrocarbons, hydrogenated aromatic hydrocarbons such as tetrahydronaphthalene and decahydronaphthalene, high molecular weight liquid paraffin, or mixtures thereof. Among them, halogenated hydrocarbons can increase yield and catalytic efficiency. preferable.
ここで、触媒効率とはバナジウム化合物の触媒としての効率を意味し、バナジウム化合物1モルから生成する塩化ビニル系重合体のモル数として定義される。 Here, the catalyst efficiency means the efficiency of the vanadium compound as a catalyst, and is defined as the number of moles of the vinyl chloride polymer produced from 1 mole of the vanadium compound.
重合温度は特に限定されるものではないが、例えば、−78℃〜100℃の範囲を選択することができる。また、重合反応圧力には特に制限はない。 Although polymerization temperature is not specifically limited, For example, the range of -78 degreeC-100 degreeC can be selected. The polymerization reaction pressure is not particularly limited.
本発明の製造方法により重合の対象となる「塩化ビニル系単量体」とは、塩化ビニル単量体単独、又は、塩化ビニル単量体及び塩化ビニル単量体と共重合可能な他のビニル系単量体の混合物であってもよい。塩化ビニル単量体と共重合可能なビニル系単量体としては、例えば、エチレン、プロピレン等のオレフィン化合物、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、アクリル酸、α−アルキルアクリル酸等の不飽和モノカルボン酸又はそのアルキルエステル類若しくはアミド類、アクリロニトリル等の不飽和ニトリル類、マレイン酸、フマル酸等の不飽和ジカルボン酸類又はそのアルキルエステル類、無水物若しくはN−置換マレイミド類、ビニルメチルエーテル、ビニルエチルエーテル等のビニルアルキルエーテル類、塩化ビニリデン等のビニリデン化合物、ブタジエン、イソプレンのような共役ジエン、1,5−ヘキサジエン、1,4−ペンタジエンのような非共役ジエン、シクロヘキセン、ノルボルネンのようなシクロオレフィン、スチレン、スチレン誘導体、N−ビニルカルバゾールのようなビニル芳香族化合物、一酸化炭素のような炭素酸化物が挙げられる。 The “vinyl chloride monomer” to be polymerized by the production method of the present invention is a vinyl chloride monomer alone or other vinyl copolymerizable with vinyl chloride monomer and vinyl chloride monomer. It may be a mixture of monomers. Examples of vinyl monomers copolymerizable with vinyl chloride monomer include olefin compounds such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, and α-alkylacrylic acid. Unsaturated monocarboxylic acids or alkyl esters or amides thereof, unsaturated nitriles such as acrylonitrile, unsaturated dicarboxylic acids such as maleic acid or fumaric acid or alkyl esters thereof, anhydrides or N-substituted maleimides, vinyl methyl Ethers, vinyl alkyl ethers such as vinyl ethyl ether, vinylidene compounds such as vinylidene chloride, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as 1,5-hexadiene and 1,4-pentadiene, cyclohexene, norbornene Like cycloolefin Emissions, styrene, styrene derivatives, vinyl aromatic compounds such as N- vinyl carbazole, carbon oxides such as carbon monoxide and the like.
また、塩化ビニル系単量体の重合において通常行われるように、適宜、熱安定性改良剤、加工性改良剤、その他の改質剤などの添加剤を重合系に添加してもよい。 In addition, as usual in the polymerization of vinyl chloride monomers, additives such as a heat stability improver, processability improver, and other modifiers may be appropriately added to the polymerization system.
本発明により得られる塩化ビニル系重合体は、例えばフィルム、シート等への成形用材料など、従来から一般的である塩化ビニル系重合体の用途に用いることができる。 The vinyl chloride polymer obtained by the present invention can be used for conventional vinyl chloride polymer applications such as materials for molding into films, sheets and the like.
以下に、本発明を実施例により説明するが、本発明はこれらの実施例により限定されるものではない。以下、実施例及び比較例で使用した単量体等、ならびに収率その他の特性の測定方法、計算方法を示す。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, the measurement method and calculation method of the monomer etc. which were used by the Example and the comparative example, and a yield other characteristic are shown.
−塩化ビニル単量体−
塩化ビニル単量体(以下、VCMとも略す)は、市販品を使用した。
-Vinyl chloride monomer-
A commercially available product was used as the vinyl chloride monomer (hereinafter also abbreviated as VCM).
−バナジウム化合物−
バナジウム(V)オキシトリエトキシドは市販品を精製しないで使用した。
-Vanadium compounds-
Vanadium (V) oxytriethoxide was used without purifying a commercial product.
V化合物1(実施例9)は文献「Journal of the American Chemical Society, 108(1986)4088-4095」に従い合成したものを精製した後使用した。 V compound 1 (Example 9) was used after purifying a compound synthesized according to the document “Journal of the American Chemical Society, 108 (1986) 4088-4095”.
V化合物2(実施例10)は文献「Bulletin of the Chemical Society of Japan, 77(2004)1849-1854」に従い合成したものを精製した後使用した。 V compound 2 (Example 10) was used after purifying a compound synthesized according to the document “Bulletin of the Chemical Society of Japan, 77 (2004) 1849-1854”.
−アルミニウム化合物・ラジカル開始剤−
アルミニウム化合物・ラジカル開始剤は、市販品を精製しないで使用した。
-Aluminum compounds and radical initiators-
The aluminum compound / radical initiator was used without purifying a commercial product.
−重合溶媒−
重合溶媒は、水素化カルシウム上で精製した後使用した。
-Polymerization solvent-
The polymerization solvent was used after purification on calcium hydride.
−塩化ビニル重合体の収率−
得られた塩化ビニル重合体の乾燥質量より算出した。
-Yield of vinyl chloride polymer-
It calculated from the dry mass of the obtained vinyl chloride polymer.
−触媒効率の計算−
触媒効率(%)={[VCM(mol/L)]×(収率(%)÷100)×62.5}÷{[遷移金属(mol/L)]×数平均分子量(Mn)}×100
-Calculation of catalyst efficiency-
Catalyst efficiency (%) = {[VCM (mol / L)] × (yield (%) ÷ 100) × 62.5} ÷ {[transition metal (mol / L)] × number average molecular weight (Mn)} × 100
−触媒活性の計算方法−
触媒活性(g−PVC/mol−遷移金属・h)={[VCM(mol/L)]×
(収率(%)÷100)×62.5}÷{[遷移金属(mol/L)]×重合時間(h)}
-Calculation method of catalyst activity-
Catalytic activity (g-PVC / mol-transition metal · h) = {[VCM (mol / L)] ×
(Yield (%) ÷ 100) × 62.5} ÷ {[transition metal (mol / L)] × polymerization time (h)}
−塩化ビニル重合体の数平均分子量及び重量平均分子量の測定−
得られた塩化ビニル重合体をゲル・パーミエーション・クロマトグラフ(東ソー(株)製)にて、溶媒としてテトラヒドロフランを用い、ポリスチレン換算値の数平均分子量(Mn)及び重量平均分子量(Mw)を測定した。
-Measurement of number average molecular weight and weight average molecular weight of vinyl chloride polymer-
The obtained vinyl chloride polymer was measured with a gel permeation chromatograph (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent and the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene. did.
ここで、Mw/Mnを分子量分布とした。 Here, Mw / Mn was defined as molecular weight distribution.
−塩化ビニル重合体の熱分解温度−
熱天秤((株)セイコー電子製、商品名TG/DTA6200)を用い、窒素気流中、10℃/minで測定した5%質量減少温度を塩化ビニル重合体の熱分解温度とした。
-Thermal decomposition temperature of vinyl chloride polymer-
Using a thermobalance (trade name TG / DTA6200, manufactured by Seiko Denshi Co., Ltd.), the 5% mass reduction temperature measured at 10 ° C./min in a nitrogen stream was defined as the thermal decomposition temperature of the vinyl chloride polymer.
〔実施例1〕
窒素置換したガラス製反応容器に、n−ヘキサンで希釈したバナジウム(V)オキシトリエトキシド(14.3mmol/L)7mLとn−ヘキサンで希釈したトリメチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
[Example 1]
Nitrogen-substituted glass reaction vessel was charged with 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and 1 mL of trimethylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例2〕
実施例1に記載のトリメチルアルミニウムに代えて、トリエチルアルミニウムを用いた以外は、実施例1と同様にして行った。
[Example 2]
The same procedure as in Example 1 was performed except that triethylaluminum was used instead of trimethylaluminum described in Example 1.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例3〕
実施例1に記載のトリメチルアルミニウムに代えて、トリイソブチルアルミニウムを用いた以外は、実施例1と同様にして行った。
Example 3
The same procedure as in Example 1 was performed except that triisobutylaluminum was used instead of trimethylaluminum described in Example 1.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例4〕
窒素置換したガラス製反応容器に、n−ヘキサンで希釈したバナジウム(V)オキシトリエトキシド(14.3mmol/L)7mLとトルエンで希釈したメチルアルミノキサン(PMAO)(商品名:PMAO−S、東ソー・ファインケム(株)製)(0.24mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
Example 4
In a glass reaction vessel purged with nitrogen, 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and methylaluminoxane (PMAO) diluted with toluene (trade name: PMAO-S, Tosoh)・ Fine Chem Co., Ltd. (0.24 mol / L) 1 mL was charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例5〕
バナジウム(V)オキシトリエトキシドの希釈溶媒を、n−ヘキサンからトルエンに代えた以外は実施例3と同様に行った。
Example 5
The same procedure as in Example 3 was performed except that the dilute solvent of vanadium (V) oxytriethoxide was changed from n-hexane to toluene.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例6〕
バナジウム(V)オキシトリエトキシドの希釈溶媒を、n−ヘキサンから四塩化炭素に代えた以外は実施例3と同様に行った。
Example 6
The same procedure as in Example 3 was performed except that the diluting solvent for vanadium (V) oxytriethoxide was changed from n-hexane to carbon tetrachloride.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例7〕
窒素置換したガラス製反応容器に、塩化メチレンで希釈したバナジウム(V)オキシトリエトキシド(28.6mmol/L)7mLとn−ヘキサンで希釈したトリイソブチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
Example 7
A glass reaction vessel purged with nitrogen was charged with 7 mL of vanadium (V) oxytriethoxide (28.6 mmol / L) diluted with methylene chloride and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例8〕
窒素置換したガラス製反応容器に、塩化メチレンで希釈したバナジウム(V)オキシトリエトキシド(14.3mmol/L)7mLとn−ヘキサンで希釈したトリイソブチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
Example 8
A glass reaction vessel purged with nitrogen was charged with 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with methylene chloride and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane. It is. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例9〕
窒素置換したガラス製反応容器に、塩化メチレンで希釈した、次式
Example 9
In a glass reaction vessel purged with nitrogen, diluted with methylene chloride,
で示される1,2−エチレンジアミノ−N,N’−ビス(3’,5’−ジ−tert−ブチルサリチリデン)オキソバナジウム(V)(表1中ではV化合物1と略す)(1.43mmol/L)7mLとn−ヘキサンで希釈したトリエチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。 1,2-ethylenediamino-N, N′-bis (3 ′, 5′-di-tert-butylsalicylidene) oxovanadium (V) (abbreviated as V compound 1 in Table 1) (1 .43 mmol / L) and 7 mL of triethylaluminum (0.1 mol / L) diluted with n-hexane were charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例10〕
窒素置換したガラス製反応容器に、塩化メチレンで希釈した、次式
Example 10
In a glass reaction vessel purged with nitrogen, diluted with methylene chloride,
で示される2−オキシ−1,3−プロパンジアミノ−N,N’−ビス(3’,5’−ジ−tert−ブチルサリチリデン)オキソバナジウム(V)(表1中ではV化合物2と略す)(1.43mmol/L)7mLとn−ヘキサンで希釈したトリエチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。 2-oxy-1,3-propanediamino-N, N′-bis (3 ′, 5′-di-tert-butylsalicylidene) oxovanadium (V) (in Table 1, V compound 2 and (Omitted) (1.43 mmol / L) 7 mL and triethylaluminum (0.1 mol / L) 1 mL diluted with n-hexane were charged. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. on calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum and adjusted to 50 ° C. The polymerization was started by dipping in a bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔比較例1〕
窒素置換したガラス製反応器に、塩化メチレンで希釈したバナジウム(V)オキシトリエトキシド(12.5mmol/L)8mLを仕込んだ後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入した。
[Comparative Example 1]
A glass reactor substituted with nitrogen was charged with 8 mL of vanadium (V) oxytriethoxide (12.5 mmol / L) diluted with methylene chloride, and then the chloride obtained by vacuum distillation at −78 ° C. over calcium hydride. 2 mL (30 mmol) of vinyl monomer was charged into the reaction vessel, the reaction vessel was sealed under vacuum, and immersed in a thermostat adjusted to 50 ° C. to initiate polymerization. When the reaction had passed for 24 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔比較例2〕
窒素置換したガラス製反応器に、塩化メチレンで希釈したトリイソブチルアルミニウム(12.5mmol/L)8mLを仕込んだ後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応器内に仕込み、該反応器を高真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入した。
[Comparative Example 2]
A glass reactor substituted with nitrogen was charged with 8 mL of triisobutylaluminum diluted with methylene chloride (12.5 mmol / L), and then 2 mL of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride. (30 mmol) was charged into the reactor, the reactor was sealed under high vacuum, and immersed in a thermostat adjusted to 50 ° C. to initiate polymerization. When the reaction had passed for 24 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔比較例3〕
窒素置換したガラス製反応容器に、トルエンで希釈したトリフェノキシ(ペンタメチルシクロペンタジエニル)チタニウム(15mmol/L)2mLとトルエンで希釈したメチルアルミノキサン(PMAO)(商品名:PMAO−S、東ソー・ファインケム(株)製)(0.3mol/L)1mLを仕込んだ。室温で10分間熟成させた後、トルエンを高真空下で除去した。その後、塩化メチレン8mLと水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、50℃に調整した恒温槽に浸し重合を開始した。反応時間が48時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
[Comparative Example 3]
In a glass reaction vessel purged with nitrogen, 2 mL of triphenoxy (pentamethylcyclopentadienyl) titanium (15 mmol / L) diluted with toluene and methylaluminoxane (PMAO) diluted with toluene (trade name: PMAO-S, Tosoh 1 mL of Finechem Co., Ltd. (0.3 mol / L) was charged. After aging for 10 minutes at room temperature, toluene was removed under high vacuum. Thereafter, 8 mL of methylene chloride and 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride were charged into the reaction vessel, and the reaction vessel was sealed under vacuum at 50 ° C. The polymerization was started by immersing in a thermostat adjusted to 1. When the reaction time reached 48 hours, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表1及び表2に示す。 Tables 1 and 2 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔実施例11〕
窒素置換したガラス製反応容器に、n−ヘキサンで希釈したバナジウム(V)オキシトリエトキシド(14.3mmol/L)7mLとn−ヘキサンで希釈したトリイソブチルアルミニウム(0.1mol/L)1mLを仕込んだ。その後、水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体2mL(30mmol)を該反応容器内に仕込み、該反応容器を真空下で溶封し、−25℃に調整した恒温槽に浸し重合を開始した。反応時間が24時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
Example 11
In a glass reaction vessel substituted with nitrogen, 7 mL of vanadium (V) oxytriethoxide (14.3 mmol / L) diluted with n-hexane and 1 mL of triisobutylaluminum (0.1 mol / L) diluted with n-hexane were added. Prepared. Thereafter, 2 mL (30 mmol) of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride was charged into the reaction vessel, and the reaction vessel was sealed under vacuum to adjust to −25 ° C. The polymerization was initiated by immersion in a thermostatic bath. When a reaction time of 24 hours passed, the vinyl chloride polymer was recovered by putting the polymerization reaction system into a large amount of methanol containing 5 vol% hydrochloric acid.
重合条件と得られた塩化ビニル重合体の評価結果を表3及び表4に示す。 Tables 3 and 4 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
〔比較例4〕
窒素置換したガラス製反応容器に、ラウロイルパーオキサイド(LPO)(ラジカル開始剤)0.379mmolと水素化カルシウム上で−78℃の真空蒸留により得た塩化ビニル単量体152mmolを仕込んだ。全量は10mLであった。該反応容器を真空下で溶封し、30℃に調整した恒温槽に浸し重合を開始した。反応が12時間経過した時点で、重合反応系を塩酸5vol%含む大量のメタノール中に投入することにより塩化ビニル重合体を回収した。
[Comparative Example 4]
A nitrogen-substituted glass reaction vessel was charged with 0.379 mmol of lauroyl peroxide (LPO) (radical initiator) and 152 mmol of vinyl chloride monomer obtained by vacuum distillation at −78 ° C. over calcium hydride. The total volume was 10 mL. The reaction vessel was sealed under vacuum and immersed in a thermostat adjusted to 30 ° C. to initiate polymerization. When the reaction had passed for 12 hours, the polymerization reaction system was put into a large amount of methanol containing 5 vol% hydrochloric acid to recover the vinyl chloride polymer.
重合条件と得られた塩化ビニル重合体の評価結果を表3及び表4に示す。 Tables 3 and 4 show the polymerization conditions and the evaluation results of the obtained vinyl chloride polymer.
本発明は熱安定性に優れた塩化ビニル系重合体を生産性良く製造するのに有用である。 The present invention is useful for producing a vinyl chloride polymer excellent in thermal stability with high productivity.
Claims (8)
(式中、iはバナジウム原子の酸化数を示し、2〜5の整数である。jは0又は1である。Zは配位子であり、ヘテロ原子でバナジウムと結合することができる有機配位子、ハロゲン配位子、置換されていてもよい単環式炭化水素配位子、又は置換されていてもよい多環式炭化水素配位子を示し、複数のZは同一でも異なっていてもよく、二以上のZが結合して該式中のバナジウム原子も構成員として環を形成していてもよい。kは配位子の数を示し、1〜5の整数である。)
で示される少なくとも一種類のバナジウム化合物(A)及び少なくとも一種類のアルミニウム化合物(B)の存在下で、塩化ビニル系単量体の重合反応を行うことを特徴とする塩化ビニル系重合体の製造方法。 General formula: V i (= O) j Z k
(Wherein i represents the oxidation number of the vanadium atom and is an integer of 2 to 5. j is 0 or 1. Z is a ligand, and an organic compound capable of binding to vanadium at a hetero atom. A ligand, a halogen ligand, an optionally substituted monocyclic hydrocarbon ligand, or an optionally substituted polycyclic hydrocarbon ligand, wherein a plurality of Z are the same or different Or two or more Z's may combine to form a ring with the vanadium atom in the formula as a member.k represents the number of ligands and is an integer of 1 to 5.)
Production of a vinyl chloride polymer, wherein a vinyl chloride monomer is polymerized in the presence of at least one vanadium compound (A) and at least one aluminum compound (B). Method.
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2019535887A (en) * | 2016-11-09 | 2019-12-12 | 株式会社ブリヂストン | High cis-1,4 block copolymer of polybutadiene and polyisoprene |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6462153B1 (en) * | 1996-04-03 | 2002-10-08 | Occidental Chemical Corporation | Method of polymerizing vinyl chloride monomer |
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---|---|---|---|---|
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JP2019535887A (en) * | 2016-11-09 | 2019-12-12 | 株式会社ブリヂストン | High cis-1,4 block copolymer of polybutadiene and polyisoprene |
US11230622B2 (en) | 2016-11-09 | 2022-01-25 | Bridgestone Corporation | High cis-1,4 block copolymers of polybutadiene and polyisoprene |
US11884767B2 (en) | 2016-11-09 | 2024-01-30 | Bridgestone Corporation | High cis-1,4 block copolymers of polybutadiene and polyisoprene |
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