JP6926878B2 - Method for Producing Polyolefin-based Graft Copolymer - Google Patents
Method for Producing Polyolefin-based Graft Copolymer Download PDFInfo
- Publication number
- JP6926878B2 JP6926878B2 JP2017179300A JP2017179300A JP6926878B2 JP 6926878 B2 JP6926878 B2 JP 6926878B2 JP 2017179300 A JP2017179300 A JP 2017179300A JP 2017179300 A JP2017179300 A JP 2017179300A JP 6926878 B2 JP6926878 B2 JP 6926878B2
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- graft copolymer
- mass
- parts
- vinyl monomer
- 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.)
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- 229920000578 graft copolymer Polymers 0.000 title claims description 94
- 229920000098 polyolefin Polymers 0.000 title claims description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000000178 monomer Substances 0.000 claims description 69
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 58
- 229920002554 vinyl polymer Polymers 0.000 claims description 52
- 150000007517 lewis acids Chemical class 0.000 claims description 35
- -1 alkyl compound Chemical class 0.000 claims description 34
- 239000002841 Lewis acid Substances 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 32
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000007870 radical polymerization initiator Substances 0.000 claims description 21
- 239000004711 α-olefin Substances 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 150000004820 halides Chemical class 0.000 claims description 12
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001350 alkyl halides Chemical class 0.000 claims description 8
- 229910052795 boron group element Inorganic materials 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001849 group 12 element Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052800 carbon group element Inorganic materials 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021480 group 4 element Inorganic materials 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 239000007788 liquid Substances 0.000 description 21
- 239000004743 Polypropylene Substances 0.000 description 18
- 238000010559 graft polymerization reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 7
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007875 V-40 Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000004581 coalescence Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052731 fluorine Chemical group 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Chemical group 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Chemical group 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-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
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- QVYIUYLZHORTBT-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2-phenylethenyl)benzene Chemical compound CC1=CC(C)=CC(C)=C1C=CC1=CC=CC=C1 QVYIUYLZHORTBT-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-butanediol Substances OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- MCVHEVPSMITDCZ-UHFFFAOYSA-N 1-butyl-3-ethenylbenzene Chemical compound CCCCC1=CC=CC(C=C)=C1 MCVHEVPSMITDCZ-UHFFFAOYSA-N 0.000 description 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 description 1
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- YBHWIVKIQYJYOH-UHFFFAOYSA-N 1-ethenyl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C=C YBHWIVKIQYJYOH-UHFFFAOYSA-N 0.000 description 1
- XIYATWBVQHWJPH-UHFFFAOYSA-N 1-ethenyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C=C XIYATWBVQHWJPH-UHFFFAOYSA-N 0.000 description 1
- XKMDZVINHIFHLY-UHFFFAOYSA-N 1-ethenyl-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(C=C)=C1 XKMDZVINHIFHLY-UHFFFAOYSA-N 0.000 description 1
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 description 1
- ZJSKEGAHBAHFON-UHFFFAOYSA-N 1-ethenyl-3-fluorobenzene Chemical compound FC1=CC=CC(C=C)=C1 ZJSKEGAHBAHFON-UHFFFAOYSA-N 0.000 description 1
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- BYYLJVQCWRRFMP-UHFFFAOYSA-N 1-ethenyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C=C)=C1 BYYLJVQCWRRFMP-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- KEZDVVCDQRDBDN-UHFFFAOYSA-N 1-ethenyl-4-fluoro-2-methylbenzene Chemical compound CC1=CC(F)=CC=C1C=C KEZDVVCDQRDBDN-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-UHFFFAOYSA-N 0.000 description 1
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- TZJQCUDHKUWEFU-UHFFFAOYSA-N 2,2-dimethylpentanenitrile Chemical compound CCCC(C)(C)C#N TZJQCUDHKUWEFU-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- VJROPLWGFCORRM-UHFFFAOYSA-N 2-methylbutan-1-amine Chemical compound CCC(C)CN VJROPLWGFCORRM-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical group CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102100040409 Ameloblastin Human genes 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100020870 La-related protein 6 Human genes 0.000 description 1
- 108050008265 La-related protein 6 Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 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
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- QLSZOQFMYAIZBM-UHFFFAOYSA-N ethenyl undecanoate Chemical compound CCCCCCCCCCC(=O)OC=C QLSZOQFMYAIZBM-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DLJMSHXCPBXOKX-UHFFFAOYSA-N n,n-dibutylprop-2-enamide Chemical compound CCCCN(C(=O)C=C)CCCC DLJMSHXCPBXOKX-UHFFFAOYSA-N 0.000 description 1
- SAEXFKSTXQREHP-UHFFFAOYSA-N n,n-dicyclohexylprop-2-enamide Chemical compound C1CCCCC1N(C(=O)C=C)C1CCCCC1 SAEXFKSTXQREHP-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- IPGRTXQKFZCLJS-UHFFFAOYSA-N n-(2-hydroxypropyl)prop-2-enamide Chemical compound CC(O)CNC(=O)C=C IPGRTXQKFZCLJS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- CYTJMBLSQUBVMS-UHFFFAOYSA-N n-[[2-cyanopropan-2-yl(formyl)amino]hydrazinylidene]formamide Chemical compound N#CC(C)(C)N(C=O)NN=NC=O CYTJMBLSQUBVMS-UHFFFAOYSA-N 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
- GZAROOOHRGKEPC-UHFFFAOYSA-N n-butyl-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)C GZAROOOHRGKEPC-UHFFFAOYSA-N 0.000 description 1
- NPFIXJIFUHTLRP-UHFFFAOYSA-N n-cyclohexyl-2-methylpropanamide Chemical compound CC(C)C(=O)NC1CCCCC1 NPFIXJIFUHTLRP-UHFFFAOYSA-N 0.000 description 1
- PMJFVKWBSWWAKT-UHFFFAOYSA-N n-cyclohexylprop-2-enamide Chemical compound C=CC(=O)NC1CCCCC1 PMJFVKWBSWWAKT-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
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- FIONWRDVKJFHRC-UHFFFAOYSA-N trimethyl(2-phenylethenyl)silane Chemical compound C[Si](C)(C)C=CC1=CC=CC=C1 FIONWRDVKJFHRC-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は、ポリオレフィン系グラフト共重合体の製造方法に関する。 The present invention relates to a method for producing a polyolefin-based graft copolymer.
従来、ポリエチレンやポリプロピレンなどのポリオレフィンを、不飽和カルボン酸あるいはその酸無水物などによってグラフト変性したポリオレフィン系グラフト共重合体は、各種樹脂の接着性付与剤又は改質剤などとして利用されている。
これらの接着性付与剤及び改質剤は、グラフト変性量の向上、グラフト構造の制御性を高めることにより、接着性、樹脂同士の相溶化などの性能をより一層向上できると期待されている。
グラフト変性量の向上及びグラフト構造の制御性の向上を目的としたグラフト共重合体の製造方法として、末端不飽和ポリプロピレンとビニル系単量体とを反応させる方法が知られている（例えば、特許文献１）。
Conventionally, a polyolefin-based graft copolymer obtained by graft-modifying a polyolefin such as polyethylene or polypropylene with an unsaturated carboxylic acid or an acid anhydride thereof has been used as an adhesive-imparting agent or a modifier for various resins.
These adhesive-imparting agents and modifiers are expected to further improve the performance such as adhesiveness and compatibility between resins by improving the amount of graft modification and improving the controllability of the graft structure.
As a method for producing a graft copolymer for the purpose of improving the amount of graft modification and improving the controllability of the graft structure, a method of reacting a terminal unsaturated polypropylene with a vinyl-based monomer is known (for example, a patent). Document 1).
ところで、通常の樹脂は疎水性であるから、接着性付与剤及び改質剤においては、有機溶剤をポリオレフィン系グラフト共重合体の分散剤又は溶剤として含むものが求められることがある。
しかし、従来のポリオレフィン系グラフト共重合体の製造方法では、有機溶剤に対する溶解性が高いグラフト共重合体は得られていなかった。
例えば特許文献１に記載のグラフト共重合体の製造方法は、ルイス酸添加系及びルイス酸無添加系で、末端不飽和ポリプロピレンとビニル系単量体とを反応させる方法である。また、特許文献１には、グラフト共重合におけるルイス酸の使用量については、単量体１モルを基準として０．０１〜１モルが好ましいと記載されている。特許文献１の実施例１９は、ルイス酸無添加系で末端不飽和ポリプロピレンとビニル単量体とをグラフト重合する例であり、この例では、末端ビニリデン基の消失率が５６．４％であり、ビニル単量体がグラフトしていない末端不飽和ポリプロピレンが多く残存していた。未反応ポリオレフィンは有機溶剤に対する溶解性が低いため、得られたグラフト共重合体の有機溶剤に対する溶解性も低い。特許文献１の実施例８は、単量体１モルを基準としてルイス酸を０．１２７モル使用してグラフト共重合体を得る例である。この例では、得られたグラフト共重合体がルイス酸残渣を多く含有しているため、アセトン抽出及びメタノール／希硫酸混合液での洗浄、メタノールでの洗浄を要した。また、グラフト共重合体がルイス酸残渣を多く含有する場合、有機溶剤に対するグラフト共重合体の溶解性が低くなる。したがって、特許文献１に記載のグラフト共重合体の製造方法は、有機溶剤に対する溶解性が高いポリオレフィン系グラフト共重合体を製造する方法とはいえなかった。
本発明は、有機溶剤に対する溶解性が高いポリオレフィン系グラフト共重合体を容易に製造できるポリオレフィン系グラフト共重合体の製造方法を提供することを目的とする。
By the way, since ordinary resins are hydrophobic, adhesive-imparting agents and modifiers may be required to contain an organic solvent as a dispersant or solvent for a polyolefin-based graft copolymer.
However, in the conventional method for producing a polyolefin-based graft copolymer, a graft copolymer having high solubility in an organic solvent has not been obtained.
For example, the method for producing a graft copolymer described in Patent Document 1 is a method of reacting a terminal unsaturated polypropylene with a vinyl-based monomer in a Lewis acid-added system and a Lewis acid-free system. Further, Patent Document 1 describes that the amount of Lewis acid used in graft copolymerization is preferably 0.01 to 1 mol based on 1 mol of the monomer. Example 19 of Patent Document 1 is an example in which a terminal unsaturated polypropylene and a vinyl monomer are graft-polymerized in a Lewis acid-free system, and in this example, the elimination rate of the terminal vinylidene group is 56.4%. , A large amount of terminally unsaturated polypropylene not grafted with vinyl monomer remained. Since the unreacted polyolefin has low solubility in an organic solvent, the solubility of the obtained graft copolymer in an organic solvent is also low. Example 8 of Patent Document 1 is an example of obtaining a graft copolymer using 0.127 mol of Lewis acid based on 1 mol of the monomer. In this example, since the obtained graft copolymer contains a large amount of Lewis acid residue, it was necessary to extract acetone, wash with a methanol / dilute sulfuric acid mixture, and wash with methanol. Further, when the graft copolymer contains a large amount of Lewis acid residue, the solubility of the graft copolymer in an organic solvent becomes low. Therefore, the method for producing a graft copolymer described in Patent Document 1 cannot be said to be a method for producing a polyolefin-based graft copolymer having high solubility in an organic solvent.
An object of the present invention is to provide a method for producing a polyolefin-based graft copolymer capable of easily producing a polyolefin-based graft copolymer having high solubility in an organic solvent.
本発明者らが鋭意研究を重ねた結果、ビニル単量体（ａ）とポリオレフィン（ｂ）からグラフト共重合体（Ｃ）を製造する際に、ビニル単量体（ａ）、ポリオレフィン（ｂ）、ラジカル重合開始剤及びルイス酸（Ｘ）の量を特定することで前記課題を解決し得ることを見出した。
すなわち、本発明は、下記の態様を含む。
［１］下記のビニル単量体（ａ）１００質量部と下記のポリオレフィン（ｂ）１〜２０００質量部とを、下記添加量のラジカル重合開始剤及び下記添加量のルイス酸の存在下で重合してグラフト共重合体（Ｃ）を得る、ポリオレフィン系グラフト共重合体の製造方法。
ビニル単量体（ａ）：アクリル酸及びその誘導体（ａ１）、メタクリル酸及びその誘導体（ａ２）、前記（ａ１）及び（ａ２）以外のビニルエステル及びその誘導体（ａ３）、並びにスチレン及びその誘導体（ａ４）から選ばれる少なくとも１種の単量体
ポリオレフィン（ｂ）：炭素数３〜２８のα−オレフィン由来の構成単位を９０質量％以上含むポリオレフィン
ラジカル重合開始剤の添加量：ビニル単量体（ａ）１００質量部に対して０．００１〜１０質量部
ルイス酸（Ｘ）の添加量：ビニル単量体（ａ）１モルに対して０．００１〜０．００９モル
［２］ルイス酸（Ｘ）が、周期表第２族、第３族、第４族、第１２族、第１３族、又は第１４族元素のハロゲン化物、アルキル化物又はハロゲン化アルキル物である、［１］に記載のポリオレフィン系グラフト共重合体の製造方法。
［３］ルイス酸（Ｘ）が、アルミニウムのハロゲン化物、アルキル化物又はハロゲン化アルキル物である、［２］に記載のポリオレフィン系グラフト共重合体の製造方法。
［４］重合の際には、重合溶媒として有機溶剤をポリオレフィン（ｂ）１００質量部に対して１００〜９９００質量部使用する、［１］〜［３］のいずれか一に記載のポリオレフィン系グラフト共重合体の製造方法。
［５］ビニル単量体（ａ）がアクリル酸及びその誘導体（ａ１）を含む、［１］〜［４］のいずれか一に記載のポリオレフィン系グラフト共重合体の製造方法。
［６］ビニル単量体（ａ）が炭素数４〜２１のアクリル酸エステルを含む、［５］に記載のポリオレフィン系グラフト共重合体の製造方法。
［７］ポリオレフィン（ｂ）が、末端不飽和基を一分子当たり０．５〜２個有する反応性ポリオレフィン（ｂ１）である、［１］〜［６］のいずれか一に記載のポリオレフィン系グラフト共重合体の製造方法。
［８］ラジカル重合開始剤が、アゾ系化合物である、［７］に記載のポリオレフィン系グラフト共重合体の製造方法。
As a result of intensive studies by the present inventors, when the graft copolymer (C) is produced from the vinyl monomer (a) and the polyolefin (b), the vinyl monomer (a) and the polyolefin (b) are produced. , It has been found that the above-mentioned problems can be solved by specifying the amounts of the radical polymerization initiator and the Lewis acid (X).
That is, the present invention includes the following aspects.
[1] 100 parts by mass of the following vinyl monomer (a) and 1 to 2000 parts by mass of the following polyolefin (b) are polymerized in the presence of the following addition amount of radical polymerization initiator and the following addition amount of Lewis acid. A method for producing a polyolefin-based graft copolymer, wherein the graft copolymer (C) is obtained.
Vinyl monomer (a): Acrylic acid and its derivative (a1), methacrylic acid and its derivative (a2), vinyl ester other than the above (a1) and (a2) and its derivative (a3), and styrene and its derivative. At least one monomer selected from (a4) Polyolefin (b): Polyolefin containing 90% by mass or more of a structural unit derived from α-olefin having 3 to 28 carbon atoms Addition amount of radical polymerization initiator: Vinyl monomer (A) 0.001 to 10 parts by mass of Lewis acid (X) added to 100 parts by mass: 0.001 to 0.009 mol [2] Lewis acid to 1 mol of vinyl monomer (a) In [1], (X) is a halide, alkylated product, or alkyl halide product of the Group 2, Group 3, Group 4, Group 12, Group 13, or Group 14 element of the periodic table. The method for producing a polyolefin-based graft copolymer according to the above method.
[3] The method for producing a polyolefin-based graft copolymer according to [2], wherein the Lewis acid (X) is a halide, alkylated or alkyl halide of aluminum.
[4] The polyolefin-based graft according to any one of [1] to [3], wherein an organic solvent is used as a polymerization solvent in an amount of 100 to 9900 parts by mass with respect to 100 parts by mass of the polyolefin (b) at the time of polymerization. Method for producing copolymer.
[5] The method for producing a polyolefin-based graft copolymer according to any one of [1] to [4], wherein the vinyl monomer (a) contains acrylic acid and a derivative (a1) thereof.
[6] The method for producing a polyolefin-based graft copolymer according to [5], wherein the vinyl monomer (a) contains an acrylic acid ester having 4 to 21 carbon atoms.
[7] The polyolefin-based graft according to any one of [1] to [6], wherein the polyolefin (b) is a reactive polyolefin (b1) having 0.5 to 2 terminal unsaturated groups per molecule. Method for producing copolymer.
[8] The method for producing a polyolefin-based graft copolymer according to [7], wherein the radical polymerization initiator is an azo-based compound.
本発明のポリオレフィン系グラフト共重合体の製造方法によれば、有機溶剤に対する溶解性が高いポリオレフィン系グラフト共重合体を容易に製造できる。 According to the method for producing a polyolefin-based graft copolymer of the present invention, a polyolefin-based graft copolymer having high solubility in an organic solvent can be easily produced.
以下、本発明の一態様を詳細に説明する。
本発明の一態様のポリオレフィン系グラフト共重合体の製造方法は、ビニル単量体（ａ）とポリオレフィン（ｂ）とを、ラジカル重合開始剤及びルイス酸（Ｘ）の存在下で重合してグラフト共重合体（Ｃ）を得る方法である。
Hereinafter, one aspect of the present invention will be described in detail.
In the method for producing a polyolefin-based graft copolymer according to one aspect of the present invention, a vinyl monomer (a) and a polyolefin (b) are polymerized and grafted in the presence of a radical polymerization initiator and a Lewis acid (X). This is a method for obtaining a copolymer (C).
＜ビニル単量体（ａ）＞
本態様で用いるビニル単量体（ａ）は、アクリル酸及びその誘導体（ａ１）、メタクリル酸及びその誘導体（ａ２）、前記（ａ１）及び（ａ２）以外のビニルエステル及びその誘導体（ａ３）、並びにスチレン及びその誘導体（ａ４）から選ばれる少なくとも１種の単量体である。
ビニル単量体（ａ）は、１種を単独で使用してもよいし、２種以上を併用してもよい。
<Vinyl monomer (a)>
The vinyl monomer (a) used in this embodiment includes acrylic acid and its derivative (a1), methacrylic acid and its derivative (a2), vinyl esters other than the above (a1) and (a2) and its derivative (a3). In addition, at least one monomer selected from styrene and its derivative (a4).
As the vinyl monomer (a), one type may be used alone, or two or more types may be used in combination.
［アクリル酸及びその誘導体（ａ１）］
アクリル酸及びその誘導体（ａ１）からなる単量体としては、下記の化合物が挙げられる。
（１）アクリル酸
（２）アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸ノルマルオクチル、アクリル酸２−エチルヘキシル、アクリル酸イソボルニル、アクリル酸４−ｔ−ブチルシクロヘキシルなどのアクリル酸エステル類
（３）アクリル酸ナトリウム、アクリル酸カリウム、アクリル酸マグネシウム、アクリル酸カルシウムなどのアクリル酸と典型金属元素からなるアクリル酸金属塩
（４）エステル残基に酸素、窒素、硫黄、珪素原子を含むアクリル酸エステル類、例えば、アクリル酸グリシジル、アクリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロキシプロピル、２−ヒドロキシ−３−フェノキシプロピルアクリレート、４−ヒドロキシブチルアクリレート、アクリロイルオキシエチルイソシアネート、メタクリロイルオキシエチルイソシアネート、３−アクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリエトキシシランなどの官能基を有するアクリル酸エステル類；ポリエチレングリコールモノアクリレート、ポリエチレングリコールポリプロピレングリコールアクリレート、ポリ（エチレングリコール−ｎ−テトラメチレングリコール）モノアクリレート、プロピレングリコールポリブチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレートなどの水酸基を有する分子量３００００以下の長鎖ポリアルキレングリコール類
（５）アクリルアミド
（６）置換基に酸素、窒素、硫黄、珪素原子を含むＮ−置換アクリルアミド、例えば、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−シクロへキシルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ，Ｎ−ジブチルアクリルアミド、Ｎ，Ｎ−ジシクロへキシルアクリルアミド、Ｎ−（２−ヒドロキシエチル）−アクリルアミド、Ｎ−（２−ヒドロキシプロピル）−アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチルアクリアミド、Ｎ−メチロールアクリルアミドなどのＮ−置換アクリルアミド
（７）アクリロニトリル
[Acrylic acid and its derivatives (a1)]
Examples of the monomer composed of acrylic acid and its derivative (a1) include the following compounds.
(1) Acrylic acid (2) Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, normal octyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, 4-t-butylcyclohexyl acrylate ( 3) Acrylic acid metal salt consisting of acrylic acid such as sodium acrylate, potassium acrylate, magnesium acrylate, calcium acrylate and typical metal elements (4) Acrylic acid containing oxygen, nitrogen, sulfur and silicon atoms in the ester residue Esters such as glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, 3 -Acrylic acid esters having functional groups such as acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane; polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate, poly (ethylene glycol-n-tetramethylene glycol) mono Long-chain polyalkylene glycols having a hydroxyl group and having a molecular weight of 30,000 or less, such as acrylate, propylene glycol polybutylene glycol monoacrylate, and polypropylene glycol monoacrylate (5) acrylamide (6) N containing oxygen, nitrogen, sulfur, and silicon atoms as substituents. -Substituted acrylamides such as N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-cyclohexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N , N-dicyclohexyl acrylamide, N- (2-hydroxyethyl) -acrylamide, N- (2-hydroxypropyl) -acrylamide, N, N-dimethylaminoethylacryamide, N-methylol acrylamide and other N-substituted acrylamides (7) Acrylonitrile
［メタクリル酸及びその誘導体（ａ２）］
メタクリル酸及びその誘導体（ａ２）からなる単量体としては、上記（ａ１）の単量体のα位の水素がメチル基などのアルキル基（好ましくは、炭素数６以下のアルキル基）によって置換された単量体が挙げられる。
[Methacrylic acid and its derivatives (a2)]
As the monomer composed of methacrylic acid and its derivative (a2), the hydrogen at the α-position of the monomer (a1) is replaced with an alkyl group such as a methyl group (preferably an alkyl group having 6 or less carbon atoms). Examples thereof include the above-mentioned monomers.
［（ａ１）及び（ａ２）以外のビニルエステル及びその誘導体（ａ３）］
前記（ａ１）及び（ａ２）以外のビニルエステル及びその誘導体（ａ３）からなる単量体としては、下記の化合物が挙げられる。
酢酸ビニル、プロピオン酸ビニル、イソラク酸ビニル、ピバリン酸ビニル、ウンデカン酸ビニル、パルミチン酸ビニルなどのビニルエステル及びその誘導体；トリメトキシビニルシランやトリエトキシビニルシランなどのアルコキシビニルシラン
[Vinyl esters other than (a1) and (a2) and their derivatives (a3)]
Examples of the monomer composed of the vinyl ester other than the above (a1) and (a2) and the derivative (a3) thereof include the following compounds.
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl isolacate, vinyl pivalate, vinyl undecanoate, vinyl palmitate and their derivatives; alkoxyvinylsilanes such as trimethoxyvinylsilane and triethoxyvinylsilane
［スチレン及びその誘導体（ａ４）］
スチレン及びその誘導体（ａ４）からなる単量体としては、下記の化合物が挙げられる。
スチレン、更には、α−メチルスチレン、ｐ−メチルスチレン、ｐ−エチルスチレン、ｐ−プロピルスチレン、ｐ−イソプロピルスチレン、ｐ−ブチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−フェニルスチレン、ｏ−メチルスチレン、ｏ−エチルスチレン、ｏ−プロピルスチレン、ｏ−イソプロピルスチレン、ｍ−メチルスチレン、ｍ−エチルスチレン、ｍ−イソプロピルスチレン、ｍ−ブチルスチレン、メシチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、３，５−ジメチルスチレンなどのアルキルスチレン類；ｐ−メトキシスチレン、ｏ−メトキシスチレン、ｍ−メトキシスチレンなどのアルコキシスチレン類；ｐ−クロロスチレン、ｍ−クロロスチレン、ｏ−ブロモスチレン、ｐ−フルオロスチレン、ｍ−フルオロスチレン、ｏ−フルオロスチレン、ｏ−メチル−ｐ−フルオロスチレンなどのハロゲン化スチレン類；トリメチルシリルスチレン、ビニル安息香酸などのスチレン及びその誘導体
[Styrene and its derivatives (a4)]
Examples of the monomer composed of styrene and its derivative (a4) include the following compounds.
Styrene, as well as α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methyl Styrene, o-ethyl styrene, o-propyl styrene, o-isopropyl styrene, m-methyl styrene, m-ethyl styrene, m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2, Alkylstyrenes such as 5-dimethylstyrene and 3,5-dimethylstyrene; alkoxystyrenes such as p-methoxystyrene, o-methoxystyrene and m-methoxystyrene; p-chlorostyrene, m-chlorostyrene and o-bromo Halogenized styrenes such as styrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene; styrenes such as trimethylsilylstyrene and vinyl benzoic acid and their derivatives.
［好ましい単量体］
グラフト共重合体（Ｃ）の製造の際には、ビニル単量体（ａ）にアクリル酸及びその誘導体（ａ１）の少なくとも１種が含まれることが好ましい。ビニル単量体（ａ）にアクリル酸及びその誘導体（ａ１）の少なくとも１種が含まれる場合、ビニル単量体（ａ）中のアクリル酸及びその誘導体（ａ１）の割合は、好ましくは１０モル％以上、より好ましくは２０モル％以上、さらに好ましくは３０モル％以上である。（ａ１）の割合が１００モル％であってもよい。ビニル単量体（ａ）が（ａ１）を含めば、ビニル単量体（ａ）とポリオレフィン（ｂ）とのグラフト共重合体（Ｃ）をより容易に製造できる。また、ビニル単量体（ａ）が（ａ１）と（ａ１）以外の単量体（ａ）、すなわち前記（ａ２）、前記（ａ３）及び前記（ａ４）とを含有する場合、（ａ１）との共重合により（ａ２）、（ａ３）及び（ａ４）のグラフト重合量を容易に向上させることができる。
アクリル酸及びその誘導体（ａ１）としては、上記の化合物の全てが好ましく、アクリル酸金属塩を除く全ての化合物がより好ましく、炭素数４〜２１のアクリル酸エステルがさらに好ましい。ビニル単量体（ａ）中の炭素数４〜２１のアクリル酸エステルの割合は、好ましくは１０モル％以上、より好ましくは２０モル％以上、さらに好ましくは３０モル％以上である。炭素数４〜２１のアクリル酸エステルの割合が１００モル％であってもよい。ビニル単量体（ａ）が炭素数４〜２１のアクリル酸エステルを含めば、ビニル単量体（ａ）とポリオレフィン（ｂ）とのグラフト共重合体（Ｃ）をさらに容易に製造できる。また、ビニル単量体（ａ）が炭素数４〜２１のアクリル酸エステルと（ａ２）、（ａ３）及び（ａ４）とを含有する場合、炭素数４〜２１のアクリル酸エステルとの共重合により（ａ２）、（ａ３）及び（ａ４）のグラフト重合量を容易に向上させることができる。
[Preferable monomer]
In the production of the graft copolymer (C), it is preferable that the vinyl monomer (a) contains at least one of acrylic acid and its derivative (a1). When the vinyl monomer (a) contains at least one of acrylic acid and its derivative (a1), the ratio of acrylic acid and its derivative (a1) in the vinyl monomer (a) is preferably 10 mol. % Or more, more preferably 20 mol% or more, still more preferably 30 mol% or more. The ratio of (a1) may be 100 mol%. If the vinyl monomer (a) contains (a1), the graft copolymer (C) of the vinyl monomer (a) and the polyolefin (b) can be more easily produced. When the vinyl monomer (a) contains a monomer (a) other than (a1) and (a1), that is, the above (a2), the above (a3) and the above (a4), (a1) By copolymerizing with (a2), (a3) and (a4), the amount of graft polymerization can be easily improved.
As the acrylic acid and its derivative (a1), all of the above compounds are preferable, all compounds except the acrylic acid metal salt are more preferable, and acrylic acid esters having 4 to 21 carbon atoms are further preferable. The ratio of the acrylic acid ester having 4 to 21 carbon atoms in the vinyl monomer (a) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more. The proportion of acrylic acid ester having 4 to 21 carbon atoms may be 100 mol%. If the vinyl monomer (a) contains an acrylic acid ester having 4 to 21 carbon atoms, the graft copolymer (C) of the vinyl monomer (a) and the polyolefin (b) can be more easily produced. When the vinyl monomer (a) contains an acrylic acid ester having 4 to 21 carbon atoms and (a2), (a3) and (a4), it is copolymerized with an acrylic acid ester having 4 to 21 carbon atoms. Therefore, the amount of graft polymerization of (a2), (a3) and (a4) can be easily improved.
＜ポリオレフィン（ｂ）＞
本態様に用いるポリオレフィン（ｂ）は、炭素数３〜２８のα−オレフィン由来の構成単位を９０質量％以上含む重合体である。
炭素数３〜２８のα−オレフィンとしては、プロピレン、１−ブテン、１−ペンテン、４−メチルペンテン−１、１−ヘキセン、１−オクテン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン及び１−イコセンなどが挙げられる。
<Polyolefin (b)>
The polyolefin (b) used in this embodiment is a polymer containing 90% by mass or more of a structural unit derived from an α-olefin having 3 to 28 carbon atoms.
Examples of α-olefins having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1 -Tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icocene and the like can be mentioned.
ポリオレフィン（ｂ）の具体例として、炭素数３〜２８のα−オレフィンから選ばれる１種の単独重合体又は２種以上の共重合体、炭素数３〜２８のα−オレフィンから選ばれる１種以上の単量体９０質量％以上１００質量％未満とエチレン０質量％超１０質量％以下とのα−オレフィン／エチレン共重合体が挙げられる。
炭素数３〜２８のα−オレフィンから選ばれる１種の単独重合体としては、プロピレン単独重合体、ブテン単独重合体、炭素数１２〜２８のαオレフィンから選ばれる１種の単独重合体が好ましい。
上記α−オレフィン／エチレン共重合体としては、α−オレフィン９２質量％以上１００質量％未満とエチレン０質量％超８質量％以下との共重合体が好ましく、α−オレフィン９５質量％以上１００質量％未満とエチレン０質量％超５質量％以下との共重合体がより好ましい。
また、ポリオレフィン（ｂ）として、プロピレン９０質量％以上１００質量％未満とエチレン及び炭素数４〜２８のα−オレフィンから選ばれる１種以上の単量体０質量％超１０質量％以下とのプロピレン系共重合体、１−ブテン９０質量％以上１００質量％未満とエチレン、プロピレン、炭素数５〜２８のαオレフィンから選ばれる１種以上の単量体０質量％超１０質量％以下とのブテン系共重合体、炭素数１２〜２８のαオレフィンの２種以上からなる共重合体、炭素数１２〜２８のα−オレフィンの１種９０質量％以上１００質量％未満とエチレン及び炭素数３〜１０のα−オレフィン０質量％超１０質量％以下との共重合体も好ましく用いられる。
上記プロピレン系共重合体においては、プロピレン９２質量％以上１００質量％未満とエチレン及び炭素数４〜２８のα−オレフィンから選ばれる１種以上の単量体０質量％超８質量％以下とのプロピレン系共重合体がより好ましく、プロピレン９５質量％以上１００質量％未満とエチレン及び炭素数４〜２８のα−オレフィンから選ばれる１種以上の単量体０質量％超５質量％以下とのプロピレン系共重合体がさらに好ましい。
As a specific example of the polyolefin (b), one homopolymer or two or more copolymers selected from α-olefins having 3 to 28 carbon atoms, and one selected from α-olefins having 3 to 28 carbon atoms. Examples thereof include α-olefin / ethylene copolymers containing 90% by mass or more and less than 100% by mass of the above-mentioned monomers and more than 0% by mass of ethylene and 10% by mass or less.
As the one homopolymer selected from the α-olefin having 3 to 28 carbon atoms, a propylene homopolymer, a butene homopolymer, and one homopolymer selected from the α-olefin having 12 to 28 carbon atoms are preferable. ..
As the α-olefin / ethylene copolymer, a copolymer of 92% by mass or more and less than 100% by mass of α-olefin and more than 0% by mass of ethylene and 8% by mass or less is preferable, and 95% by mass or more and 100% by mass of α-olefin. A copolymer of less than% and more than 0% by mass of ethylene and 5% by mass or less is more preferable.
Further, as the polyolefin (b), propylene containing 90% by mass or more and less than 100% by mass of propylene and one or more monomers selected from ethylene and α-olefin having 4 to 28 carbon atoms is more than 0% by mass and 10% by mass or less. Butene, a system copolymer, 1-butene 90% by mass or more and less than 100% by mass, and one or more monomers selected from ethylene, propylene, and α-olefin having 5 to 28 carbon atoms in an amount of more than 0% by mass and 10% by mass or less. A system copolymer, a copolymer composed of two or more kinds of α-olefins having 12 to 28 carbon atoms, one kind of α-olefin having 12 to 28 carbon atoms, 90% by mass or more and less than 100% by mass, ethylene and 3 to 3 carbon atoms. A copolymer of 10 α-olefins in an amount of more than 0% by mass and 10% by mass or less is also preferably used.
In the above propylene-based copolymer, 92% by mass or more and less than 100% by mass of propylene and one or more monomers selected from ethylene and α-olefin having 4 to 28 carbon atoms are more than 0% by mass and 8% by mass or less. Propylene-based copolymers are more preferable, and propylene is 95% by mass or more and less than 100% by mass, and one or more monomers selected from ethylene and α-olefin having 4 to 28 carbon atoms, which are more than 0% by mass and 5% by mass or less. Propylene-based copolymers are more preferred.
本態様で用いるポリオレフィン（ｂ）は、末端不飽和基を一分子当たり０．５〜２個有する反応性ポリオレフィン（ｂ１）であってもよい。反応性ポリオレフィン（ｂ１）を用いると、ラジカル重合開始剤によって本態様のグラフト共重合体（Ｃ）をより容易に製造することができる。
反応性ポリオレフィン（ｂ）は、具体的には末端不飽和基を一分子当たり０．５〜２個有するポリオレフィンのことである。当該定義は、反応性ポリオレフィン（ｂ１）中に含まれる全てのポリオレフィン分子が末端不飽和基を有して反応性を有するとは限らないことを意味している。また、当該定義は、反応性ポリオレフィン（ｂ１）は一分子当たり２個以上の不飽和基を有する成分、例えば両末端に不飽和基を含有するような成分を含有することも意味している。
上記反応性ポリオレフィン（ｂ１）における末端不飽和基の数は、上記のように一分子当たり０．５〜２個が好ましく、０．６〜２個がより好ましく、０．８〜２個がさらに好ましい。末端不飽和基の数が０．５個以上であれば、不飽和基の濃度が高くなり、グラフト共重合体が得られやすくなる。一分子当たりの末端不飽和基の数が２個より多い反応性ポリオレフィン（ｂ１）は製造が容易ではない。
The polyolefin (b) used in this embodiment may be a reactive polyolefin (b1) having 0.5 to 2 terminal unsaturated groups per molecule. When the reactive polyolefin (b1) is used, the graft copolymer (C) of this embodiment can be more easily produced by the radical polymerization initiator.
The reactive polyolefin (b) is specifically a polyolefin having 0.5 to 2 terminal unsaturated groups per molecule. This definition means that not all polyolefin molecules contained in the reactive polyolefin (b1) have a terminal unsaturated group and are reactive. The definition also means that the reactive polyolefin (b1) contains a component having two or more unsaturated groups per molecule, for example, a component containing unsaturated groups at both ends.
As described above, the number of terminal unsaturated groups in the reactive polyolefin (b1) is preferably 0.5 to 2 per molecule, more preferably 0.6 to 2, and further preferably 0.8 to 2. preferable. When the number of terminal unsaturated groups is 0.5 or more, the concentration of unsaturated groups becomes high, and a graft copolymer can be easily obtained. Reactive polyolefins (b1) with more than two terminal unsaturated groups per molecule are not easy to produce.
上記末端不飽和基の数は、核磁気共鳴スペクトル法、赤外線吸収スペクトル法、臭素化法等によって測定することができる。
ポリオレフィン鎖がポリプロピレンであり、末端不飽和基が１−プロペニル（ビニル）基およびビニリデン基である場合の末端不飽和基の定量は、次のようにして行う。
一分子当たりの末端ビニル基数及び一分子当たりの末端ビニリデン基数は、１Ｈ−ＮＭＲから得られる１−プロペニル（ビニル）末端濃度［Ｖｉ］と、ビニリデン末端濃度［Ｖｄ］を、ゲルパーミエイションクロマトグラフィ（ＧＰＣ）より求めた数平均分子量（Ｍｎ）から得られる全ポリマー鎖数に対する割合として、下式を用いて算出する。
（一分子当たりの末端ビニル基数）＝（Ｍｎ／４２）×２×［Ｖｉ］／１０００
（一分子当たりの末端ビニリデン基数）＝（Ｍｎ／４２）×２×［Ｖｄ］／１０００
（ただし、Ｍｎは、ＧＰＣにより求めた数平均分子量である。）
The number of terminal unsaturated groups can be measured by a nuclear magnetic resonance spectrum method, an infrared absorption spectrum method, a bromination method, or the like.
When the polyolefin chain is polypropylene and the terminal unsaturated group is a 1-propenyl (vinyl) group and a vinylidene group, the quantification of the terminal unsaturated group is performed as follows.
The number of terminal vinyl groups per molecule and the number of terminal vinylidene groups per molecule are the 1 -propenyl (vinyl) terminal concentration [Vi] obtained from 1 H-NMR and the vinylidene terminal concentration [Vd] obtained by gel permeation chromatography. It is calculated using the following formula as a ratio to the total number of polymer chains obtained from the number average molecular weight (Mn) obtained from (GPC).
(Number of terminal vinyl groups per molecule) = (M n / 42) x 2 x [Vi] / 1000
(Number of terminal vinylidene groups per molecule) = (M n / 42) × 2 × [Vd] / 1000
(However, M n is a number average molecular weight obtained by GPC.)
ここで、１Ｈ−ＮＭＲによる１−プロペニル（ビニル）末端濃度［Ｖｉ］およびビニリデン末端濃度［Ｖｄ］の測定法の詳細は、以下の通りである。
試料３０ｍｇを重水素化１，１，２，２−テトラクロロエタン１ｇに溶解させた後、ＮＭＲサンプル管（直径５ｍｍ）に注入し、１００℃で測定する。ケミカルシフトは、重水素化１，１，２，２−テトラクロロエタンのピークを６ｐｐｍに設定する。他のプロトンピークのケミカルシフトは、重水素化１，１，２，２−テトラクロロエタンのピークを基準とする。
装置：Ｖａｒｉａｎ ＵＮＩＴＹ ＩＮＯＶＡ ５００
パルス照射角度：４５度
パルス照射時間：１１．２５μｓ
積算回数：１０，０００回
観測域：−０．７５ｐｐｍから１５．２５ｐｐｍ
Here, the details of the method for measuring the 1-propenyl (vinyl) terminal concentration [Vi] and the vinylidene terminal concentration [Vd] by 1 H-NMR are as follows.
After dissolving 30 mg of the sample in 1 g of deuterated 1,1,2,2-tetrachloroethane, it is injected into an NMR sample tube (diameter 5 mm) and measured at 100 ° C. The chemical shift sets the peak of deuterated 1,1,2,2-tetrachloroethane to 6 ppm. Chemical shifts of other proton peaks are relative to the peak of deuterated 1,1,2,2-tetrachloroethane.
Equipment: Varian UNITY INOVA 500
Pulse irradiation angle: 45 degrees Pulse irradiation time: 11.25 μs
Number of integrations: 10,000 observation range: -0.75ppm to 15.25ppm
［Ｖｉ］は、下記構造式（１−ａ）のメチン基の１Ｈ（プロトン１）が５．８〜５．９ｐｐｍに、メチレン基の２Ｈ（プロトン２）が５．０〜５．１ｐｐｍに検出されることを利用し、［Ｖｄ］は、下記構造式（１−ｂ）のメチレン基の２Ｈ（プロトン３）が４．９〜５．０ｐｐｍに検出されることを利用して、それぞれ全骨格形成炭素１０００個に対する個数として下式のように算出する。ここで全骨格形成炭素とはプロピレン連鎖のメチル炭素以外の全ての炭素原子を意味し、プロピレン連鎖の６Ｈ（メチン、メチレン、メチル基のプロトン）が０．６〜２．３ｐｐｍに観測されることから、［全骨格形成炭素数］＝［プロピレン連鎖のピーク強度］／３の式で算出される。
［Ｖｉ］＝（［メチレン基の２Ｈ（プロトン２）のピーク強度］／２）／［全骨格形成炭素数］×１０００
［Ｖｄ］＝（［メチレン基の２Ｈ（プロトン３）のピーク強度］／２）／［全骨格形成炭素数］×１０００
In [Vi], 1H (proton 1) of the methine group of the following structural formula (1-a) was detected at 5.8 to 5.9 ppm, and 2H (proton 2) of the methylene group was detected at 5.0 to 5.1 ppm. [Vd] is the whole skeleton by utilizing the fact that 2H (proton 3) of the methylene group of the following structural formula (1-b) is detected at 4.9 to 5.0 ppm. Calculate as the following formula as the number for 1000 formed carbons. Here, the total skeleton-forming carbon means all carbon atoms other than the methyl carbon of the propylene chain, and 6H (methine, methylene, methyl group protons) of the propylene chain is observed at 0.6 to 2.3 ppm. Therefore, it is calculated by the formula [total number of carbon atoms forming the skeleton] = [peak intensity of propylene chain] / 3.
[Vi] = ([peak intensity of 2H (proton 2) of methylene group] / 2) / [total number of skeleton-forming carbon atoms] × 1000
[Vd] = ([Peak intensity of 2H (proton 3) of methylene group] / 2) / [Total skeleton-forming carbon number] × 1000
ポリオレフィン（ｂ）は、数平均分子量（Ｍｎ）が、好ましくは２５０〜４０００００、より好ましくは５００〜２０００００、さらに好ましくは１０００〜１０００００である。数平均分子量（Ｍｎ）が２５０以上であれば、得られるグラフト共重合体（Ｃ）においてポリオレフィンに対する密着性等の機能がより発現しやすくなり、４０００００以下であればグラフト共重合体（Ｃ）作製時に重合溶液が均一になりやすくグラフト化を起こしやすくする。 The polyolefin (b) has a number average molecular weight (M n ) of preferably 250 to 400,000, more preferably 500 to 200,000, and even more preferably 1,000 to 100,000. When the number average molecular weight (M n ) is 250 or more, the obtained graft copolymer (C) is more likely to exhibit functions such as adhesion to polyolefin, and when it is 400,000 or less, the graft copolymer (C) is easily exhibited. During production, the polymerization solution tends to be uniform and grafting is likely to occur.
ポリオレフィン（ｂ）は分子量分布が狭いほど好ましい。具体的には、ポリオレフィン（ｂ）の分子量分布（Ｍｗ／Ｍｎ）は４．０以下が好ましく、３．５以下がより好ましく、３．０以下がさらに好ましい。ポリオレフィン（ｂ）の分子量分布が狭ければ、グラフト共重合体において、ポリオレフィン（ｂ）が形成する連鎖における連鎖長のばらつきが少なくなるため、構造が高度に制御されたグラフト共重合体を容易に製造できる。 The narrower the molecular weight distribution of the polyolefin (b), the more preferable it is. Specifically, the molecular weight distribution (M w / M n ) of the polyolefin (b) is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. If the molecular weight distribution of the polyolefin (b) is narrow, the variation in the chain length in the chain formed by the polyolefin (b) is small in the graft copolymer, so that the graft copolymer having a highly controlled structure can be easily obtained. Can be manufactured.
分子量分布（Ｍｗ／Ｍｎ）は、ゲルパーミエイションクロマトグラフィ（ＧＰＣ）法により、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）を測定することにより求めることができる。本明細書における分子量の測定法、測定機器の詳細は以下の通りである。 The molecular weight distribution (M w / M n ) can be determined by measuring the weight average molecular weight (M w ) and the number average molecular weight (M n ) by the gel permeation chromatography (GPC) method. The details of the method for measuring the molecular weight and the measuring device in the present specification are as follows.
測定器：ＰＬ−２１０
カラム：東ソー社製ＴＳＫｇｅｌ ＧＭＨ−ＨＴ（３０ｃｍ×４本）
測定条件
溶媒：ｏ−ジクロロベンゼン
測定温度：１３５℃
流速：１．０ｍｌ／分
試料濃度：０．１質量％
試料の調製：測定用ポリマー約２０ｍｇを、ジブチルヒドロキシトルエンを含有するｏ−ジクロロベンゼン（ジブチルヒドロキシトルエン濃度＝０．５ｇ／Ｌ）に溶解し、ポリマー濃度が０．１質量％になるように調製して混合溶液を得る。該混合溶液を１３５℃に加熱し、ポリマーを溶解させた後、グラスフィルターを用いて濾過して試料を調製する。
分子量の算出：標準試料として市販の単分散のポリスチレンを使用し、該ポリスチレン標準試料およびプロピレン系重合体の粘度式から、保持時間と分子量に関する校正曲線を作成し、該校正曲線に基づいて分子量を求める。分子量への換算に使用する粘度式：［η］＝Ｋ×Ｍαは、以下の数値を用いる。
ポリスチレン：Ｋ＝１．３８×１０−４、α＝０．７０
プロピレン重合体：Ｋ＝１．０３×１０−４、α＝０．７８
Measuring instrument: PL-210
Column: Tosoh TSKgel GMH-HT (30 cm x 4)
Measurement conditions Solvent: o-dichlorobenzene Measurement temperature: 135 ° C
Flow velocity: 1.0 ml / min Sample concentration: 0.1% by mass
Sample preparation: Approximately 20 mg of the polymer for measurement is dissolved in o-dichlorobenzene (dibutylhydroxytoluene concentration = 0.5 g / L) containing dibutylhydroxytoluene, and the polymer concentration is adjusted to 0.1% by mass. To obtain a mixed solution. The mixed solution is heated to 135 ° C. to dissolve the polymer, and then filtered using a glass filter to prepare a sample.
Calculation of molecular weight: Using a commercially available monodisperse polystyrene as a standard sample, create a calibration curve for retention time and molecular weight from the viscosity formula of the polystyrene standard sample and propylene-based polymer, and calculate the molecular weight based on the calibration curve. Ask. Viscosity formula used for conversion to molecular weight: [η] = K × M α uses the following numerical values.
Polystyrene: K = 1.38 × 10 -4 , α = 0.70
Propene polymer: K = 1.03 × 10 -4 , α = 0.78
グラフト重合反応におけるポリオレフィン（ｂ）の使用量としては、ビニル単量体（ａ）１００質量部に対して通常は１〜２０００質量部であり、好ましくは１〜１０００質量部、より好ましくは１〜５００質量部、さらに好ましくは１〜１００質量部、特に好ましくは１〜８０質量部である。ポリオレフィン（ｂ）の使用量が１質量部以上であると、グラフト重合において、ビニル単量体（ａ）の単独重合体の生成量が少なくなる。ポリオレフィン（ｂ）の使用量が２０００質量部以下であると、グラフト共重合体（Ｃ）におけるビニル単量体（ａ）から形成される連鎖部の組成比が増加し、有機溶剤に対するグラフト共重合体（Ｃ）の溶解性がより向上する。 The amount of the polyolefin (b) used in the graft polymerization reaction is usually 1 to 2000 parts by mass, preferably 1 to 1000 parts by mass, and more preferably 1 to 1 part by mass with respect to 100 parts by mass of the vinyl monomer (a). It is 500 parts by mass, more preferably 1 to 100 parts by mass, and particularly preferably 1 to 80 parts by mass. When the amount of the polyolefin (b) used is 1 part by mass or more, the amount of the homopolymer of the vinyl monomer (a) produced is reduced in the graft polymerization. When the amount of the polyolefin (b) used is 2000 parts by mass or less, the composition ratio of the chain portion formed from the vinyl monomer (a) in the graft copolymer (C) increases, and the graft copolymer weight with respect to the organic solvent increases. The solubility of the coalescence (C) is further improved.
＜グラフト重合＞
［ラジカル重合開始剤］
本態様のグラフト重合に用いられるラジカル重合開始剤としては特に制限はなく、従来公知のラジカル重合開始剤、例えば、各種アゾ系化合物、有機過酸化物などの中から適宜選択して用いることができる。アゾ系化合物、有機過酸化物の両化合物はともに好適なラジカル重合開始剤である。
ポリオレフィン（ｂ）として反応性ポリオレフィン（ｂ１）を用い、反応性ポリオレフィン（ｂ１）の末端不飽和基でグラフト反応を進行させて構造を高度に制御したグラフト共重合体（Ｃ）を製造する場合には、ラジカル重合開始剤はアゾ系化合物が好ましい。
アゾ系化合物としては、例えば、２，２−アゾビス（イソブチロニトリル）（ＡＩＢＮ）、２，２−アゾビス（２−メチルブチロニトリル）（ＡＭＢＮ）、２，２−アゾビス（２，４−ジメチルバレロニトリル）（ＡＤＶＮ）、１，１−アゾビス（１−シクロヘキサンカルボニトリル）（ＡＣＨＮ、Ｖ−４０）、ジメチル−２，２−アゾビスイソブチレート（ＭＡＩＢ）、１，１−アゾビス（１−アセトキシ−１−フェニルエタン）、２，２−アゾビス（２−メチルブチルアミド）、２，２−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２−アゾビス（２，４，４−トリメチルペンタン）、２−シアノ−２−プロピルアゾホルムアミド、２，２−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２，２−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）などが挙げられる。
<Graft polymerization>
[Radical polymerization initiator]
The radical polymerization initiator used for the graft polymerization of this embodiment is not particularly limited, and can be appropriately selected from conventionally known radical polymerization initiators such as various azo compounds and organic peroxides. .. Both the azo compound and the organic peroxide compound are suitable radical polymerization initiators.
When reactive polyolefin (b1) is used as the polyolefin (b) and the graft reaction is allowed to proceed with the terminal unsaturated group of the reactive polyolefin (b1) to produce a graft copolymer (C) having a highly controlled structure. The radical polymerization initiator is preferably an azo compound.
Examples of the azo compound include 2,2-azobis (isobutyronitrile) (AIBN), 2,2-azobis (2-methylbutyronitrile) (AMBN), and 2,2-azobis (2,4-). Dimethylvaleronitrile) (ADVN), 1,1-azobis (1-cyclohexanecarbonitrile) (ACHN, V-40), dimethyl-2,2-azobisisobutyrate (MAIB), 1,1-azobis (1) -Acetoxy-1-phenylethane), 2,2-azobis (2-methylbutylamide), 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4) , 4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2-azobis (N-butyl-2-methylpropionamide), 2,2-azobis (N-cyclohexyl-2-methylpropionamide) And so on.
これらのアゾ系化合物は反応温度や反応溶媒に応じて適宜選択することが好ましい。反応温度が低ければ、低温分解型のアゾ系化合物を用いることが好ましく、反応温度が高温であれば、高温分解型のアゾ系化合物を用いることが好ましい。しかし、反応温度が低い場合に高温分解型のアゾ系化合物を用いても構わないし、反応温度が高い場合に低温分解型のアゾ系化合物を用いても構わない。 It is preferable to appropriately select these azo compounds according to the reaction temperature and the reaction solvent. If the reaction temperature is low, it is preferable to use a low-temperature decomposition type azo compound, and if the reaction temperature is high, it is preferable to use a high-temperature decomposition type azo compound. However, when the reaction temperature is low, a high temperature decomposition type azo compound may be used, and when the reaction temperature is high, a low temperature decomposition type azo compound may be used.
有機過酸化物としては、例えば、ジベンゾイルパーオキシド，ジ−８，５，５−トリメチルヘキサノイルパーオキシド，ジラウロイルパーオキシド，ジデカノイルパーオキシド，ジ（２，４−ジクロロベンゾイル）パーオキシドなどのジアシルパーオキシド類、ｔ−ブチルヒドロパーオキシド，キュメンヒドロパーオキシド，ジイソプロピルベンゼンヒドロパーオキシド，２，５−ジメチルヘキサン−２，５−ジヒドロパーオキシドなどのヒドロパーオキシド類、ジ−ｔ−ブチルパーオキシド，ジクミルパーオキシド，２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン，２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、α，α’ビス（ｔ−ブチルパーオキシ）ジイソプロピルベンゼンなどのジアルキルパーオキシド類、１，１−ビス−ｔ−ブチルパーオキシ−３，３，５−トリメチルシクロヘキサン，２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール類、ｔ−ブチルパーオキシオクトエート，ｔ−ブチルパーオキシピバレート，ｔ−ブチルパーオキシネオデカノエート，ｔ−ブチルパーオキシベンゾエートなどのアルキルパーエステル類、ジ−２−エチルヘキシルパーオキシジカーボネート，ジイソプロピルパーオキシジカーボネート，ジ−ｓｅｃ−ブチルパーオキシジカーボネート，ｔ−ブチルパーオキシイソプロピルカーボネートなどのパーオキシカーボネート類などが挙げられる。 Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl Peroxide, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, Dialkyl peroxides such as α, α'bis (t-butylperoxy) diisopropylbenzene, 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-) Butyl peroxy) Peroxy ketals such as butane, alkyl peresters such as t-butyl peroxyoctate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butylperoxybenzoate , Di-2-ethylhexyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate, peroxy carbonates such as t-butyl peroxyisopropyl carbonate and the like.
上記のラジカル重合開始剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
グラフト重合反応におけるラジカル重合開始剤の使用量はグラフト共重合体（Ｃ）の所望物性に応じて適宜選定される。ラジカル重合開始剤の具体的な使用量はビニル単量体（ａ）１００質量部に対し、通常０．００１〜１０質量部であり、好ましくは０．００５〜８質量部、より好ましくは０．０１〜７質量部、さらに好ましくは０．１〜５質量部である。ラジカル重合開始剤の使用量が０．００１質量部以上であれば、グラフト重合が容易に進行するが、１０質量部を超えて添加すると、グラフト重合に寄与しないラジカル重合開始剤が増え、無駄なコストを生じる。
The above radical polymerization initiator may be used alone or in combination of two or more.
The amount of the radical polymerization initiator used in the graft polymerization reaction is appropriately selected according to the desired physical properties of the graft copolymer (C). The specific amount of the radical polymerization initiator used is usually 0.001 to 10 parts by mass, preferably 0.005 to 8 parts by mass, and more preferably 0. parts by mass with respect to 100 parts by mass of the vinyl monomer (a). It is 01 to 7 parts by mass, more preferably 0.1 to 5 parts by mass. If the amount of the radical polymerization initiator used is 0.001 part by mass or more, the graft polymerization easily proceeds, but if it is added in excess of 10 parts by mass, the amount of the radical polymerization initiator that does not contribute to the graft polymerization increases, which is useless. Incur costs.
［ルイス酸（Ｘ）］
本態様のグラフト重合に用いられるルイス酸（Ｘ）としては、電子対を受容可能な全ての物質を使用することができる。ルイス酸（Ｘ）のなかでも、周期表第２族、第３族、第４族又は第１３族元素のハロゲン化物、アルキル化物、ハロゲン化アルキル物が好ましい。ハロゲン化物としては具体的には、塩化物、臭化物、フッ化物、ヨウ化物が挙げられ、本態様におけるアルキル化物は、炭素数１〜２０のアルキル基によってアルキル化されたものであり、例えば、メチル化物、エチル化物、プロピル化物、ブチル化物、ペンチル化物、ヘキシル化物、オクチル化物、デシル化物等が挙げられる。
ルイス酸（Ｘ）が、周期表第２族、第３族、第４族、第１２族、第１３族、又は第１４族元素のハロゲン化物、アルキル化物又はハロゲン化アルキル物であれば、グラフト共重合体（Ｃ）においてグラフト化していないポリオレフィン量がより減少して、有機溶剤に対するグラフト共重合体（Ｃ）の溶解性がより高くなる。
[Lewis acid (X)]
As the Lewis acid (X) used for the graft polymerization of this embodiment, any substance that can accept an electron pair can be used. Among the Lewis acids (X), halides, alkylated products, and alkyl halides of the elements of Group 2, Group 3, Group 4, or Group 13 of the periodic table are preferable. Specific examples of the halide include chloride, bromide, fluoride, and iodide. The alkylated product in this embodiment is alkylated by an alkyl group having 1 to 20 carbon atoms, and is, for example, methyl. Examples thereof include products, ethyl products, propyl products, butyl products, pentyl products, hexyl products, octyl products, and decyl products.
If the Lewis acid (X) is a halide, alkylated or alkyl halide of the Group 2, Group 3, Group 4, Group 12, Group 13 or Group 14 elements of the Periodic Table, the graft The amount of ungrafted polyolefin in the copolymer (C) is further reduced, and the solubility of the grafted copolymer (C) in the organic solvent is higher.
ルイス酸（Ｘ）の具体例としては、下記のものが挙げられる。
第２族元素のハロゲン化物として、例えば、塩化マグネシウム、塩化カルシウム、これら化合物の塩素原子を臭素原子又はフッ素原子に置き換えた化合物等が挙げられる。
第２族元素のアルキル化物として、ブチルエチルマグネシウム等が挙げられる。
第１２族元素のハロゲン化物として、例えば、塩化亜鉛、この化合物の塩素原子を臭素原子又はフッ素原子に置き換えた化合物等が挙げられる。
第１２族元素のアルキル化物として、例えば、ジエチル亜鉛等が挙げられる。
第１３族元素のハロゲン化物として、例えば、三塩化アルミニウム、三塩化硼素、三塩化ガリウム、これら化合物の塩素原子を臭素原子又はフッ素原子に置き換えた化合物等が挙げられる。
第１３族元素のアルキル化物として、例えば、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、トリノルマルへキシルアルミニウム、トリメチル硼素、トリエチル硼素、トリエチルガリウム、トリメチルガリウム等が挙げられる。
第１３族元素のハロゲン化アルキル化物として、例えば、ジエチルアルミニウムモノクロリド、エチルアルミニウムジクロリド、エチルアルミニウムセスキクロリド等が挙げられる。
第１４族元素のハロゲン化物として、例えば、四塩化珪素、この化合物の塩素原子を臭素原子又はフッ素原子に置き換えた化合物等が挙げられる。
Specific examples of Lewis acid (X) include the following.
Examples of the halide of the Group 2 element include magnesium chloride, calcium chloride, and a compound in which the chlorine atom of these compounds is replaced with a bromine atom or a fluorine atom.
Examples of the alkylated product of the Group 2 element include butyl ethyl magnesium and the like.
Examples of the halide of the Group 12 element include zinc chloride, a compound in which the chlorine atom of this compound is replaced with a bromine atom or a fluorine atom, and the like.
Examples of the alkylated product of the Group 12 element include diethylzinc and the like.
Examples of the halide of the Group 13 element include aluminum trichloride, boron trichloride, gallium trichloride, and compounds in which the chlorine atom of these compounds is replaced with a bromine atom or a fluorine atom.
Examples of alkylated products of Group 13 elements include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, trimethylboron, triethylboron, triethylgallium, trimethylgallium and the like.
Examples of the halogenated alkylated product of the Group 13 element include diethylaluminum monochloroide, ethylaluminum dichloride, ethylaluminum sesquichloride and the like.
Examples of the halide of the Group 14 element include silicon tetrachloride, a compound in which the chlorine atom of this compound is replaced with a bromine atom or a fluorine atom, and the like.
上記ルイス酸（Ｘ）のなかでも、アルミニウムのハロゲン化物、アルキル化物又はハロゲン化アルキル物が好ましい。ルイス酸（Ｘ）がアルミニウムのハロゲン化物、アルキル化物又はハロゲン化アルキル物であれば、グラフト共重合体（Ｃ）中のグラフト化していないポリオレフィンの生成量がより減少し、グラフト共重合体（Ｃ）の有機溶剤に対する溶解性がより高くなる。
さらに、上記ルイス酸（Ｘ）のなかでも、三塩化アルミニウム、三臭化アルミニウム、三フッ化アルミニウム、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、トリノルマルへキシルアルミニウム、ジエチルアルミニウムモノクロリド、エチルアルミニウムジクロリド、エチルアルミニウムセスキクロリドが好ましい。
特に上記ルイス酸のなかでも、取扱い性の面から、三塩化アルミニウム、三臭化アルミニウム、三フッ化アルミニウムがより好ましい。
ルイス酸（Ｘ）は１種を単独で使用してもよいし、２種以上を併用してもよい。
Among the Lewis acids (X), aluminum halides, alkylates or alkyl halides are preferable. If the Lewis acid (X) is a halide, alkylated or alkyl halide of aluminum, the amount of ungrafted polyolefin produced in the graft copolymer (C) is further reduced, and the graft copolymer (C) is produced. ) Is more soluble in organic solvents.
Further, among the above-mentioned Lewis acids (X), aluminum trichloride, aluminum tribromide, aluminum trifluoride, trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, Ethylaluminum sesquichloride is preferred.
In particular, among the above Lewis acids, aluminum trichloride, aluminum tribromide, and aluminum trifluoride are more preferable from the viewpoint of handleability.
One type of Lewis acid (X) may be used alone, or two or more types may be used in combination.
グラフト重合反応におけるルイス酸（Ｘ）の使用量としては、ビニル単量体（ａ）１モルに対し、０．００１〜０．００９モル、好ましくは０．００２〜０．００９モル、より好ましくは０．００３〜０．００９モル、さらに好ましくは０．００６〜０．００９モルである。
ルイス酸（Ｘ）の使用量が０．００１モル以上であることにより、ビニル単量体（ａ）がグラフト重合していないポリオレフィン量が減少するため、有機溶剤に対する溶解性が高いグラフト共重合体（Ｃ）が得られやすくなる。一方、ルイス酸の使用量が０．００９モル以下であることにより、得られるグラフト共重合体（Ｃ）においてルイス酸残渣由来の濁り又は着色が起こり難くなる。
グラフト重合する際のルイス酸（Ｘ）の添加方法には特に制限はない。例えば、ビニル単量体（ａ）及びラジカル重合開始剤を添加する前にポリオレフィン（ｂ）にルイス酸（Ｘ）を添加してもよい。また、ラジカル重合開始剤を添加する前に、ビニル単量体（ａ）及びポリオレフィン（ｂ）を含む重合系にルイス酸（Ｘ）を添加してもよい。また、ビニル単量体（ａ）とルイス酸（Ｘ）とを予め混合させたものをポリオレフィン（ｂ）に添加してもよい。
The amount of Lewis acid (X) used in the graft polymerization reaction is 0.001 to 0.009 mol, preferably 0.002 to 0.009 mol, more preferably 0.002 to 0.009 mol, based on 1 mol of the vinyl monomer (a). It is 0.003 to 0.009 mol, more preferably 0.006 to 0.009 mol.
When the amount of Lewis acid (X) used is 0.001 mol or more, the amount of polyolefin in which the vinyl monomer (a) is not graft-polymerized is reduced, so that the graft copolymer having high solubility in an organic solvent is used. (C) can be easily obtained. On the other hand, when the amount of Lewis acid used is 0.009 mol or less, turbidity or coloring derived from the Lewis acid residue is less likely to occur in the obtained graft copolymer (C).
The method of adding Lewis acid (X) during graft polymerization is not particularly limited. For example, Lewis acid (X) may be added to the polyolefin (b) before adding the vinyl monomer (a) and the radical polymerization initiator. Further, before adding the radical polymerization initiator, Lewis acid (X) may be added to the polymerization system containing the vinyl monomer (a) and the polyolefin (b). Further, a mixture of a vinyl monomer (a) and a Lewis acid (X) in advance may be added to the polyolefin (b).
［重合溶媒］
グラフト重合の際、重合溶媒は使用せずに無溶媒としてもよいが、重合しやすさの点から、有機溶剤を用いることが好ましい。
有機溶剤としては、例えば、トルエン、ブタン、ペンタン、ヘキサン、シクロヘキサンなどの炭化水素系溶剤；クロロベンゼン、ジクロロベンゼン、トリクロロベンゼンなどのハロゲン化炭化水素系溶剤；液化α−オレフィンなどが挙げられる。有機溶剤は１種を単独で使用してもよいし、２種以上を併用してもよい。
有機溶剤のなかでも、ビニル単量体（ａ）及びポリオレフィン（ｂ）の両方を溶解させるものが好ましい。グラフト重合の際にビニル単量体（ａ）及びポリオレフィン（ｂ）の両方が有機溶剤に溶解した状態にすれば、ビニル単量体（ａ）とポリオレフィン（ｂ）との反応性が高くなる。
重合反応での有機溶剤の使用量としては、ポリオレフィン（ｂ）１００質量部に対して１００〜９９００質量部が好ましく、１００〜６０００質量部がより好ましく、１００〜４０００質量部がさらに好ましい。有機溶剤の使用量が１００質量部以上であれば、重合系が均一化されて重合が容易に進行する。有機溶剤の使用量が９９００質量部以下であれば、重合系中の反応物の濃度が高くなり、重合の進行が速くなる。
[Polymerization solvent]
At the time of graft polymerization, a solvent-free polymerization solvent may be used without using a polymerization solvent, but it is preferable to use an organic solvent from the viewpoint of easiness of polymerization.
Examples of the organic solvent include hydrocarbon solvents such as toluene, butane, pentane, hexane and cyclohexane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; and liquefied α-olefins. One type of organic solvent may be used alone, or two or more types may be used in combination.
Among the organic solvents, those that dissolve both the vinyl monomer (a) and the polyolefin (b) are preferable. If both the vinyl monomer (a) and the polyolefin (b) are dissolved in the organic solvent during the graft polymerization, the reactivity between the vinyl monomer (a) and the polyolefin (b) becomes high.
The amount of the organic solvent used in the polymerization reaction is preferably 100 to 9900 parts by mass, more preferably 100 to 6000 parts by mass, still more preferably 100 to 4000 parts by mass with respect to 100 parts by mass of the polyolefin (b). When the amount of the organic solvent used is 100 parts by mass or more, the polymerization system is homogenized and the polymerization easily proceeds. When the amount of the organic solvent used is 9900 parts by mass or less, the concentration of the reactant in the polymerization system becomes high, and the progress of polymerization becomes fast.
［重合温度］
グラフト重合の重合温度を高温とした場合、ポリオレフィン（ｂ）の分解による分子量低下及び粘度低下を招き、架橋反応などによるゲルの発生が起こり易くなる。一方、グラフト重合の重合温度をある程度低温とした場合、分子量低下及び粘度低下が生じにくく、架橋反応などの副反応も進行しにくい。これらのことから、重合温度としては、通常０〜３００℃の範囲内であり、好ましくは２０〜２００℃、より好ましくは２０〜１５０℃、さらに好ましくは２０〜１４０℃、最も好ましくは２０〜１３０℃である。
[Polymerization temperature]
When the polymerization temperature of the graft polymerization is set to a high temperature, the decomposition of the polyolefin (b) causes a decrease in molecular weight and viscosity, and gel formation due to a cross-linking reaction or the like is likely to occur. On the other hand, when the polymerization temperature of graft polymerization is set to a certain low temperature, a decrease in molecular weight and a decrease in viscosity are unlikely to occur, and side reactions such as a cross-linking reaction are also unlikely to proceed. From these facts, the polymerization temperature is usually in the range of 0 to 300 ° C., preferably 20 to 200 ° C., more preferably 20 to 150 ° C., further preferably 20 to 140 ° C., and most preferably 20 to 130 ° C. ℃.
［重合時間］
重合時間としては、０．１〜１０時間が好ましい。重合時間が０．１時間以上であれば、グラフト重合反応の進行度が大きくなり、グラフト共重合体（Ｃ）を充分に製造できる。しかし、重合時間が１０時間を超えると、反応の進行がほぼ止まり、転化率の向上が見込めないため、生産性低下を招く。
[Polymerization time]
The polymerization time is preferably 0.1 to 10 hours. When the polymerization time is 0.1 hour or more, the progress of the graft polymerization reaction becomes large, and the graft copolymer (C) can be sufficiently produced. However, if the polymerization time exceeds 10 hours, the progress of the reaction is almost stopped, and the conversion rate cannot be expected to be improved, resulting in a decrease in productivity.
＜グラフト共重合体（Ｃ）＞
上記製造方法により得られたグラフト共重合体（Ｃ）は、ビニル単量体（ａ）とポリオレフィン（ｂ）とのグラフト共重合体である。ポリオレフィン（ｂ）は有機溶剤難溶性であり、有機溶剤に溶解しにくいが、ビニル単量体（ａ）の重合体は有機溶剤可溶性であり、有機溶剤に対する溶解性は高い。本態様においては、ポリオレフィン（ｂ）にビニル単量体（ａ）が共重合することでポリオレフィン（ｂ）の有機溶剤難溶性を相対的に抑えて、グラフト共重合体（Ｃ）全体としての、有機溶剤に対する溶解性を向上させている。
有機溶剤に対する溶解性が高い本態様のグラフト共重合体（Ｃ）は、ポリオレフィン系樹脂用の接着性付与剤、塗料・コーティング材料、粘着剤、分散剤、インキバインダー、成形剤などとして好適に使用できる。
<Graft copolymer (C)>
The graft copolymer (C) obtained by the above production method is a graft copolymer of a vinyl monomer (a) and a polyolefin (b). The polyolefin (b) is sparingly soluble in an organic solvent and is difficult to dissolve in an organic solvent, but the polymer of the vinyl monomer (a) is soluble in an organic solvent and has high solubility in an organic solvent. In this embodiment, the vinyl monomer (a) is copolymerized with the polyolefin (b) to relatively suppress the poor solubility of the polyolefin (b) in the organic solvent, so that the graft copolymer (C) as a whole is subjected to. It improves the solubility in organic solvents.
The graft copolymer (C) of this embodiment having high solubility in an organic solvent is suitably used as an adhesive-imparting agent for polyolefin resins, paints / coating materials, pressure-sensitive adhesives, dispersants, ink binders, molding agents, and the like. can.
以下、実施例により本発明を説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の例において「部」は「質量部」を意味し、ビニル単量体（ａ）の仕込み量を基準である１００質量部とした。また、以下の例において使用した略号の意味は下記の通りである。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In the following example, "parts" means "parts by mass", and the amount of the vinyl monomer (a) charged was set to 100 parts by mass as a reference. The meanings of the abbreviations used in the following examples are as follows.
・ＢＡ：ｎ−ブチルアクリレート
・ＩＢＸＡ：イソボルニルアクリレート
・ＭＭＡ：メチルメタクリレート
・反応性ＰＰ：反応性ポリプロピレン（合成品、Ｍｎ＝１０６００、Ｍｗ／Ｍｎ＝２．１１、一分子当たりの末端ビニル基数＝１．１個）
・熱分解ＰＰ：熱分解ポリプロピレン（市販品、Ｍｎ＝７５００、Ｍｗ／Ｍｎ＝２．０２、一分子当たりの末端ビニリデン基数＝１．３個）
・Ｖ−４０：１，１’−アゾビス（１−シクロヘキサンカルボニトリル）
・ＡｌＣｌ３：三塩化アルミニウム
-BA: n-Butyl acrylate-IBXA: Isobornyl acrylate-MMA: Methyl methacrylate-Reactive PP: Reactive polypropylene (synthetic product, M n = 10600, M w / M n = 2.11 per molecule Number of terminal vinyl groups = 1.1)
-Pyrolytic PP: Pyrolytic polypropylene (commercially available, M n = 7500, M w / M n = 2.02, number of terminal vinylidene groups per molecule = 1.3)
V-40: 1,1'-azobis (1-cyclohexanecarbonitrile)
-AlCl 3 : Aluminum trichloride
［実施例１］
撹拌装置、冷却管を備えた重合装置にトルエン２２２部（２０ｇ）を投入し、そのトルエンに窒素バブリング（流量１００ｍＬ／ｍｉｎ）を１０分間施した。次に、重合装置内の空間に窒素を流量５０ｍＬ／ｍｉｎで流す窒素フローを施した。その後、ＡｌＣｌ３を、ビニル単量体（ａ）である後述のＢＡ１モルに対して０．００８モル（０．０７４９ｇ）と、反応性ＰＰ１１部（１ｇ）とを重合装置内に投入した。窒素フローを継続し、重合装置を外温９５℃で加熱しながら重合装置内を撹拌することで、ＡｌＣｌ３と反応性ＰＰをトルエンに溶解させた。
次いで、ＢＡ１００部（９ｇ）にＶ−４０ １．１部（０．１ｇ）を溶解させて重合性混合物を調製した。この重合性混合物に１０分間の窒素バブリング（流量５０ｍＬ／ｍｉｎ）を施した後、重合装置に投入することで重合反応を開始した。窒素雰囲気下、外温９５℃で重合反応を継続させ、反応開始から５時間経過後に重合装置を冷却して反応を停止させて、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 1]
222 parts (20 g) of toluene was put into a polymerization apparatus equipped with a stirrer and a cooling tube, and nitrogen bubbling (flow rate 100 mL / min) was applied to the toluene for 10 minutes. Next, a nitrogen flow was applied in which nitrogen was flowed at a flow rate of 50 mL / min in the space inside the polymerization apparatus. Then, 0.008 mol (0.0749 g) of AlCl 3 and 11 parts (1 g) of the reactive PP were put into the polymerization apparatus with respect to 1 mol of BA described later as the vinyl monomer (a). AlCl 3 and reactive PP were dissolved in toluene by continuing the nitrogen flow and stirring the inside of the polymerization apparatus while heating the polymerization apparatus at an outside temperature of 95 ° C.
Next, 1.1 parts (0.1 g) of V-40 was dissolved in 100 parts (9 g) of BA to prepare a polymerizable mixture. The polymerizable mixture was subjected to nitrogen bubbling (flow rate 50 mL / min) for 10 minutes and then charged into a polymerization apparatus to initiate a polymerization reaction. The polymerization reaction is continued in a nitrogen atmosphere at an outside temperature of 95 ° C., and after 5 hours have passed from the start of the reaction, the polymerization apparatus is cooled to stop the reaction, and the graft copolymer (C) is contained in toluene. A coalescence-containing liquid was obtained.
［実施例２］
ＡｌＣｌ３の添加量を表１に示す量に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 2]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that the amount of AlCl 3 added was changed to the amount shown in Table 1.
［実施例３］
反応性ＰＰ１１部を熱分解ＰＰ１１部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 3]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 11 parts of the reactive PP was changed to 11 parts of the pyrolyzed PP.
［実施例４］
反応性ＰＰ１１部を熱分解ＰＰ１１部に変更した以外は実施例２と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 4]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 2 except that 11 parts of the reactive PP was changed to 11 parts of the pyrolyzed PP.
［実施例５］
トルエン、反応性ＰＰ、Ｖ−４０、ＡｌＣｌ３の添加量を表１に示す量に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 5]
In the same manner as in Example 1 except that the amounts of toluene, reactive PP, V-40, and AlCl 3 added were changed to the amounts shown in Table 1, the graft copolymer (C) was contained in toluene. A coalescence-containing liquid was obtained.
［実施例６］
ＢＡ１００部をＩＢＸＡ１００部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 6]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 100 parts of BA was changed to 100 parts of IBXA.
［実施例７，８］
トルエン、反応性ＰＰ、Ｖ−４０、ＡｌＣｌ３の添加量を表１に示す量に変更した以外は実施例６と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Examples 7 and 8]
In the same manner as in Example 6 except that the amounts of toluene, reactive PP, V-40, and AlCl 3 added were changed to the amounts shown in Table 1, the graft copolymer (C) was contained in toluene. A coalescence-containing liquid was obtained.
［実施例９］
ＢＡ１００部をＢＡ８９部及びＭＭＡ１１部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 9]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 100 parts of BA were changed to 89 parts of BA and 11 parts of MMA.
［実施例１０］
ＢＡ１００部をＢＡ６７部及びＭＭＡ３３部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 10]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 100 parts of BA were changed to 67 parts of BA and 33 parts of MMA.
［実施例１１］
ＢＡ１００部をＢＡ３３部及びＭＭＡ６７部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 11]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 100 parts of BA were changed to 33 parts of BA and 67 parts of MMA.
［実施例１２］
ＢＡ１００部をＭＭＡ１００部に変更した以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Example 12]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that 100 parts of BA was changed to 100 parts of MMA.
［比較例１，２］
ＡｌＣｌ３の添加量を表２に示す量とした以外は実施例１と同様にして、トルエン中にグラフト共重合体（Ｃ）が含まれるグラフト共重合体含有液を得た。
[Comparative Examples 1 and 2]
A graft copolymer-containing liquid containing the graft copolymer (C) in toluene was obtained in the same manner as in Example 1 except that the amount of AlCl 3 added was set to the amount shown in Table 2.
＜評価＞
得られた各例のグラフト共重合体含有液において、トルエンに対するグラフト共重合体（Ｃ）の溶解性を、以下のようにグラフト共重合体含有液の光透過性を観察することで評価した。
グラフト共重合体含有液を１００℃に加熱して均一状態にし、無色のガラス製スクリューバイアル管（日電理化硝子社製、ＳＶ−１０）に高さが１ｃｍになるように投入した。次いで、グラフト共重合体含有液の入ったバイアル管を室温まで冷やした後、白紙に印刷した丸印“◎”（ＭＳゴシック、２０ｐｔ）の上に置いた。
室温（２３℃）中で厚み１ｃｍのグラフト共重合体含有液を通して、印刷した丸印を見たときの丸印の視認の程度により、グラフト共重合体含有液の光透過性を以下の基準で評価した。評価結果を表１，２に示す。
Ａ：丸印がはっきり見え、光透過性はとても高い、Ｂ：丸印がややぼけて見えるが視認可能であり、光透過性は高い、Ｃ：丸印がぼけて見える又は色みがかかって丸印が見え、光透過性は低い
光透過性が高い程、トルエンに対するグラフト共重合体の溶解性が高い。
<Evaluation>
In the obtained graft copolymer-containing liquids of each example, the solubility of the graft copolymer (C) in toluene was evaluated by observing the light transmittance of the graft copolymer-containing liquid as follows.
The graft copolymer-containing liquid was heated to 100 ° C. to make it uniform, and charged into a colorless glass screw vial tube (manufactured by Nichiden Rika Glass Co., Ltd., SV-10) so as to have a height of 1 cm. Next, the vial tube containing the graft copolymer-containing liquid was cooled to room temperature and then placed on a circle “⊚” (MS Gothic, 20 pt) printed on a blank sheet of paper.
The light transmittance of the graft copolymer-containing liquid is determined according to the following criteria according to the degree of visibility of the printed circles when the printed circles are viewed through the graft copolymer-containing liquid having a thickness of 1 cm at room temperature (23 ° C.). evaluated. The evaluation results are shown in Tables 1 and 2.
A: Circle mark is clearly visible and light transmission is very high, B: Circle mark looks slightly blurred but visible and light transmission is high, C: Circle mark looks blurry or tinted Circles are visible and light transmission is low. The higher the light transmission, the higher the solubility of the graft copolymer in toluene.
ルイス酸（Ｘ）をビニル単量体（ａ）１モルに対して０．００１モル以上０．００９モル以下添加した実施例１〜１２では、グラフト共重合体含有液の光透過性が高く、有機溶剤に対するグラフト共重合体（Ｃ）の溶解性が高かった。
これに対し、ルイス酸（Ｘ）を添加しなかった比較例１では、グラフト共重合体含有液は白濁し光透過性が低く、グラフト共重合体（Ｃ）の有機溶剤に対する溶解性が低かった。
ルイス酸（Ｘ）の添加量がビニル単量体（ａ）１モルに対して０．００９モルより多かった比較例２では、グラフト共重合体含有液は赤みを呈しており光透過性が低く、グラフト共重合体（Ｃ）の有機溶剤に対する溶解性が低かった。
In Examples 1 to 12 in which Lewis acid (X) was added in an amount of 0.001 mol or more and 0.009 mol or less with respect to 1 mol of the vinyl monomer (a), the light transmittance of the graft copolymer-containing liquid was high. The solubility of the graft copolymer (C) in an organic solvent was high.
On the other hand, in Comparative Example 1 in which Lewis acid (X) was not added, the graft copolymer-containing liquid became cloudy and had low light transmittance, and the solubility of the graft copolymer (C) in an organic solvent was low. ..
In Comparative Example 2 in which the amount of Lewis acid (X) added was more than 0.009 mol with respect to 1 mol of the vinyl monomer (a), the graft copolymer-containing liquid was reddish and had low light transmittance. , The solubility of the graft copolymer (C) in an organic solvent was low.
Claims (8)
ビニル単量体（ａ）：アクリル酸及びその誘導体（ａ１）、メタクリル酸及びその誘導体（ａ２）、前記（ａ１）及び（ａ２）以外のビニルエステル及びその誘導体（ａ３）、並びにスチレン及びその誘導体（ａ４）から選ばれる少なくとも１種の単量体
ポリオレフィン（ｂ）：炭素数３〜２８のα−オレフィン由来の構成単位を９０質量％以上含むポリオレフィン
ラジカル重合開始剤の添加量：ビニル単量体（ａ）１００質量部に対して０．００１〜１０質量部
ルイス酸（Ｘ）の添加量：ビニル単量体（ａ）１モルに対して０．００１〜０．００９モル 100 parts by mass of the following vinyl monomer (a) and 1 to 2000 parts by mass of the following polyolefin (b) are polymerized and grafted in the presence of the following addition amount of radical polymerization initiator and the following addition amount of Lewis acid. A method for producing a polyolefin-based graft copolymer, which obtains the copolymer (C).
Vinyl monomer (a): Acrylic acid and its derivative (a1), methacrylic acid and its derivative (a2), vinyl ester other than the above (a1) and (a2) and its derivative (a3), and styrene and its derivative. At least one monomer selected from (a4) Polyolefin (b): Polyolefin containing 90% by mass or more of a structural unit derived from α-olefin having 3 to 28 carbon atoms Addition amount of radical polymerization initiator: Vinyl monomer (A) 0.001 to 10 parts by mass of Lewis acid (X) added to 100 parts by mass: 0.001 to 0.009 mol to 1 mol of vinyl monomer (a)
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