JP4213099B2 - Modified polypropylene resin - Google Patents
Modified polypropylene resin Download PDFInfo
- Publication number
- JP4213099B2 JP4213099B2 JP2004269942A JP2004269942A JP4213099B2 JP 4213099 B2 JP4213099 B2 JP 4213099B2 JP 2004269942 A JP2004269942 A JP 2004269942A JP 2004269942 A JP2004269942 A JP 2004269942A JP 4213099 B2 JP4213099 B2 JP 4213099B2
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene resin
- weight
- meth
- parts
- modified polypropylene
- 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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- -1 polypropylene Polymers 0.000 title claims description 99
- 239000004743 Polypropylene Substances 0.000 title claims description 92
- 229920001155 polypropylene Polymers 0.000 title claims description 86
- 229920005989 resin Polymers 0.000 title claims description 86
- 239000011347 resin Substances 0.000 title claims description 86
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 4
- 230000014509 gene expression Effects 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- 150000003254 radicals Chemical class 0.000 description 20
- 239000000178 monomer Substances 0.000 description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 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 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-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
- 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 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- JVXHNZWBWQKDDA-UHFFFAOYSA-N (2,5-dichlorobenzoyl) 2,5-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=C(Cl)C(C(=O)OOC(=O)C=2C(=CC=C(Cl)C=2)Cl)=C1 JVXHNZWBWQKDDA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-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
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-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
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- VYNQWGXTLZDYFX-UHFFFAOYSA-N 1-benzoylperoxyhexyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(CCCCC)OOC(=O)C1=CC=CC=C1 VYNQWGXTLZDYFX-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HQLILHPGWSURBT-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]acetic acid Chemical compound CC(C)(C)OCC(O)=O HQLILHPGWSURBT-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 1
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-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
- AUJLDZJNMXNESO-UHFFFAOYSA-N 3-ethylhex-3-ene Chemical compound CCC=C(CC)CC AUJLDZJNMXNESO-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- FHHSSXNRVNXTBG-UHFFFAOYSA-N 3-methylhex-3-ene Chemical compound CCC=C(C)CC FHHSSXNRVNXTBG-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- RGTDIFHVRPXHFT-UHFFFAOYSA-N 3-methylnon-3-ene Chemical compound CCCCCC=C(C)CC RGTDIFHVRPXHFT-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- YCTDZYMMFQCTEO-UHFFFAOYSA-N 3-octene Chemical compound CCCCC=CCC YCTDZYMMFQCTEO-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- KZJIOVQKSAOPOP-UHFFFAOYSA-N 5,5-dimethylhex-1-ene Chemical compound CC(C)(C)CCC=C KZJIOVQKSAOPOP-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl 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])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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- SOVOPSCRHKEUNJ-UHFFFAOYSA-N dec-4-ene Chemical compound CCCCCC=CCCC SOVOPSCRHKEUNJ-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
- 238000000354 decomposition reaction Methods 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
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl 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])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])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001196 nonadecyl 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])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])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl 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])C([H])([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
- 125000002958 pentadecyl 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])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
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は、不飽和カルボン酸、その無水物または誘導体がグラフト共重合した変性ポリプロピレン樹脂およびその製造方法に関するものである。更に詳しくは、不飽和カルボン酸、その無水物または誘導体の含有量と分子量とのバランスおよび他の素材との親和性に優れ、かつ製造コストが安価である変性ポリプロピレン樹脂およびその製造方法に関する。 The present invention relates to a modified polypropylene resin obtained by graft copolymerization of an unsaturated carboxylic acid, an anhydride or a derivative thereof, and a method for producing the same. More specifically, the present invention relates to a modified polypropylene resin having an excellent balance between the content and molecular weight of an unsaturated carboxylic acid, its anhydride or derivative, and affinity with other materials, and a low production cost, and a method for producing the same.
ポリプロピレン樹脂は低密度で機械物性、耐薬品性等に優れ、かつ成形加工が容易であることから、自動車部品、家電部品、各種容器、シート、フィルム、繊維等の幅広い分野で使用されている。また性能を向上させる手段として、他の素材との複合が行われ、例えば無機充填剤との組み合せによる剛性および耐熱性に優れた複合材、あるいは他の樹脂フィルムとの組み合せによる複合フィルムなど多くのものが知られている。 Polypropylene resin is used in a wide range of fields such as automobile parts, home appliance parts, various containers, sheets, films, and fibers because it has a low density, excellent mechanical properties, chemical resistance, and the like, and can be easily molded. In addition, as a means to improve performance, it is combined with other materials, for example, a composite material excellent in rigidity and heat resistance in combination with an inorganic filler, or a composite film in combination with another resin film. Things are known.
しかしながら、ポリプロピレン樹脂は炭化水素を主体とする骨格であり、その分子鎖中に極性基を含有していないため、他の素材に対する相溶性が乏しく、このためそのままでは塗料や接着剤の直接塗布、あるいは金属との接着または極性樹脂との複合化などが困難であるので、ポリプロピレン樹脂の改質が行われている。 However, polypropylene resin is a skeleton mainly composed of hydrocarbons, and since it does not contain polar groups in its molecular chain, it has poor compatibility with other materials. Alternatively, since it is difficult to bond with a metal or to combine with a polar resin, the polypropylene resin is modified.
他の素材に対する相溶性を改質するため、ポリプロピレン樹脂に無水マレイン酸などの極性基を有するビニルモノマーまたはその誘導体をグラフトする方法が提案されている。しかし、一般的に、ポリプロピレン樹脂に不飽和カルボン酸またはその誘導体およびラジカル開始剤を作用させると、ポリプロピレン分子鎖中にラジカルが形成され、不飽和カルボン酸またはその誘導体のグラフト共重合が進行してグラフト変性物が得られるが、これと同時にポリプロピレン分子鎖切断による分子量低下が起こる。このため、グラフト変性物の分子量は変性前のポリプロピレン樹脂の分子量よりかなり小さくなる。分子量が大きく低下すると、ポリプロピレン樹脂が本来有している機械物性などが失われるので、ポリプロピレン分子鎖中に形成されたラジカルに、効率よく不飽和カルボン酸またはその誘導体を付加させる必要がある。 In order to modify the compatibility with other materials, a method of grafting a vinyl monomer having a polar group such as maleic anhydride or a derivative thereof onto a polypropylene resin has been proposed. However, generally, when an unsaturated carboxylic acid or its derivative and a radical initiator are allowed to act on a polypropylene resin, a radical is formed in the polypropylene molecular chain, and the graft copolymerization of the unsaturated carboxylic acid or its derivative proceeds. A graft modified product is obtained, but at the same time, the molecular weight is reduced due to polypropylene molecular chain scission. For this reason, the molecular weight of the graft modified product is considerably smaller than the molecular weight of the polypropylene resin before modification. When the molecular weight is greatly reduced, the mechanical properties inherent to the polypropylene resin are lost, so it is necessary to efficiently add an unsaturated carboxylic acid or a derivative thereof to a radical formed in the polypropylene molecular chain.
したがって、得られた変性ポリプロピレン樹脂の分子量が大きく、高グラフト量での変性ポリプロピレン樹脂を低コストで効率よく製造することができる方法は、工業的に非常に重要となる。 Therefore, a method capable of efficiently producing a modified polypropylene resin with a high molecular weight at a low cost is very important industrially because the obtained modified polypropylene resin has a large molecular weight.
ところで、特開昭４４−１５４２２号公報および特開昭５２−３０５４５号公報では、炭化水素系の溶媒中で結晶性ポリプロピレン樹脂を加熱溶解あるいは膨潤させた後、無水マレイン酸およびラジカル開始剤を作用させて変性ポリプロピレン樹脂を調製している。この製造方法によれば無水マレイン酸を効率的にグラフトすることができ、未グラフトの無水マレイン酸含有量の少ない変性ポリプロピレン樹脂が得られる。しかしながら、製造工程が煩雑であるため工業的に有効な方法とはいえない。 In JP-A-44-15422 and JP-A-52-30545, a crystalline polypropylene resin is heated and dissolved or swollen in a hydrocarbon solvent, and then maleic anhydride and a radical initiator are used. Thus, a modified polypropylene resin is prepared. According to this production method, maleic anhydride can be efficiently grafted, and an ungrafted modified polypropylene resin having a low content of maleic anhydride can be obtained. However, it is not an industrially effective method because the manufacturing process is complicated.
また特開平６−３１３０７８号公報では、押出機中で高濃度の無水マレイン酸をグラフトした変性ポリプロピレン樹脂により、ナイロンとの相溶性を改良している。しかしながら、この変性ポリプロピレン樹脂は分子量が非常に小さいため機械物性の改良効果は期待できない。さらに変性ポリプロピレン樹脂中に未グラフトの無水マレイン酸が残存するため、他の素材との接着性に悪影響を及ぼす可能性がある。 In JP-A-6-313078, compatibility with nylon is improved by a modified polypropylene resin grafted with a high concentration of maleic anhydride in an extruder. However, since this modified polypropylene resin has a very small molecular weight, it cannot be expected to improve the mechanical properties. Furthermore, ungrafted maleic anhydride remains in the modified polypropylene resin, which may adversely affect the adhesion to other materials.
さらに特開２００２−２５６０２３号公報および特開２００２−３０８９４７号公報、押出機中で結晶性ポリプロピレンに無水マレイン酸等の極性基およびラジカル開始剤を作用させて極性基をグラフトさせた変性ポリプロピレン樹脂を調製している。しかしながら、このような変性ポリプロピレン樹脂中の極性基含有量が少なく、相溶性改良効果は小さい。
本発明は、分子量の低下が少なく、不飽和カルボン酸および／又はその誘導体のグラフト量が多く、かつ生産性に優れた変性ポリプロピレン樹脂を提供する。 The present invention provides a modified polypropylene resin having a low molecular weight, a large amount of unsaturated carboxylic acid and / or a derivative thereof, and excellent productivity.
本発明は、例えば次の変性ポリプロピレン樹脂およびその製造方法を提供する。
（１）ポリプロピレン樹脂（Ａ）１００重量部に対し、無水マレイン酸（Ｂ）０．１〜１０重量部、エステル部の炭素数が７以下の（メタ）アクリル酸エステル（Ｃ）０．５〜５重量部、およびラジカル開始剤（Ｄ）０．０１〜１０重量部により変性した変性ポリプロ
ピレン樹脂であって、１３５℃デカリン中で測定される固有粘度［η］を［η］MPP（ｄ
ｌ／ｇ）、ポリプロピレン樹脂（Ａ）の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＰＰ）（℃）、および変性ポリプロピレン樹脂の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＭＰＰ）（℃）、無水マレイン酸（Ｂ）のグラフト量をＭＧ（重量％）、およびエステル部の炭素数が７以下の（メタ）アクリル酸エステル（Ｃ）のグラフト量をＥＧ（重量％）とした場合に、下記関係式（i）、（ii）、（iii）および(iv)を満足することを特徴とする変性ポリプロピレン樹脂。
The present invention provides, for example, the following modified polypropylene resin and a method for producing the same.
(1) 0.1 to 10 parts by weight of maleic anhydride (B) with respect to 100 parts by weight of polypropylene resin (A), (meth) acrylic acid ester (C) having an ester part having 7 or less carbon atoms 0.5 to 5 parts by weight and a modified polypropylene resin modified with 0.01 to 10 parts by weight of a radical initiator (D), wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is [η] MPP (d
l / g), the melting point of the polypropylene resin (A) measured by a differential scanning calorimeter (DSC) Tm (PP) (° C.), and the melting point of a modified polypropylene resin measured by a differential scanning calorimeter (DSC) The graft amount of Tm (MPP) (° C.), the graft amount of maleic anhydride (B) is MG (% by weight), and the graft amount of (meth) acrylate ester (C) having 7 or less carbon atoms in the ester moiety is EG (weight) %)), A modified polypropylene resin characterized by satisfying the following relational expressions (i), (ii), (iii) and (iv):
０．７≦［η］MPP ≦ ２．０ ・・・（i）
０≦Ｔｍ（ＰＰ）−Ｔｍ（ＭＰＰ）≦１５ ・・・（ii）
０．８≦ＭＧ≦５ ・・・（iii）
０＜ＥＧ／ＭＧ ≦１ ・・・（iv）
0.7 ≦ [η] MPP ≦ 2.0 (i)
0 ≦ Tm (PP) −Tm (MPP) ≦ 15 (ii)
0.8 ≦ MG ≦ 5 (iii)
0 <EG / MG ≦ 1 (iv)
（２）１３５℃デカリン中で測定される固有粘度［η］が１〜１５ｄｌ／ｇであるポリプロピレン樹脂（Ａ）１００重量部に対して、無水マレイン酸（Ｂ）０．１〜１０重量部、メタクリル酸ベンジル（Ｃ）０．５〜５重量部、およびラジカル開始剤（Ｄ）０．０１〜１０重量部を含む混合物を溶融混合してグラフト共重合した上記（１）に記載の変性ポリプロピレン樹脂。
(2) 0.1 to 10 parts by weight of maleic anhydride (B) with respect to 100 parts by weight of the polypropylene resin (A) having an intrinsic viscosity [η] measured in decalin of 135 ° C. of 1 to 15 dl / g, The modified polypropylene resin according to the above (1), wherein a mixture containing 0.5 to 5 parts by weight of benzyl methacrylate (C) and 0.01 to 10 parts by weight of a radical initiator (D) is melt-mixed and graft copolymerized. .
本発明の変性ポリプロピレン樹脂は、従来の変性ポリプロピレン樹脂に比べて、高グラフト量、かつ高分子量であるので、他の素材との親和性が改良され、かつ機械物性も良好である。このような特性を有する本発明の変性ポリプロピレン樹脂は、単独でも使用可能であり、自動車、家電等の工業部品分野；フィルム、シート等の包装分野；その他容器分野、繊維分野などの分野において幅広く使用することができる。 Since the modified polypropylene resin of the present invention has a higher graft amount and higher molecular weight than conventional modified polypropylene resins, it has improved affinity with other materials and good mechanical properties. The modified polypropylene resin of the present invention having such characteristics can be used alone and widely used in the fields of industrial parts such as automobiles and home appliances; the field of packaging of films and sheets; the field of containers and the field of textiles. can do.
本発明で使用する変性前のポリプロピレン樹脂（Ａ）はプロピレンの単独重合体であってもよいし、少量の他のモノマーとの共重合体であってもよいが、プロピレン単独重合体が好ましい。共重合体の場合、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。 The polypropylene resin (A) before modification used in the present invention may be a propylene homopolymer or a copolymer with a small amount of other monomers, but a propylene homopolymer is preferred. In the case of a copolymer, it may be a random copolymer or a block copolymer.
本発明で使用する変性前のポリプロピレン樹脂（Ａ）は、［η］は１〜１５ ｄｌ／ｇ、好ましくは３〜１２ ｄｌ／ｇであるポリプロピレン樹脂が望ましい。 The polypropylene resin (A) before modification used in the present invention is desirably a polypropylene resin having [η] of 1 to 15 dl / g, preferably 3 to 12 dl / g.
ポリプロピレン樹脂としては、プロピレン単独重合体又はエチレン−プロピレンランダム共重合体、プロピレン−α-オレフィンランダム共重合体、プロピレンブロック共重合体があげられる。また、これらの重合体をブレンドしてもかまわない。前述のα-オレフィンの具体例としては、１−ブテン、２−メチル−１−プロペン、２−メチル−１−ブテン、３−メチル−１−ブテン、１−ヘキセン、２−エチル−１−ブテン、２，３−ジメチル−１−ブテン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３，３−ジメチル−１−ブテン、１−ヘプテン、メチル−１−ヘキセン、ジメチル−１−ペンテン、エチル−１−ペンテン、トリメチル−１−ブテン、メチルエチル−１−ブテン、１−オクテン、メチル−１−ペンテン、エチル−１−ヘキセン、ジメチル−１−ヘキセン、プロピル−１−ヘプテン、メチルエチル−１−ヘプテン、トリメチル−１−ペンテン、プロピル−１−ペンテン、ジエチル−１−ブテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン等をあげることができる。 Examples of the polypropylene resin include a propylene homopolymer, an ethylene-propylene random copolymer, a propylene-α-olefin random copolymer, and a propylene block copolymer. Further, these polymers may be blended. Specific examples of the α-olefin include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 2-ethyl-1-butene. 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl -1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1- Hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-u Decene, 1-dodecene, etc. can be mentioned.
本発明で使用する不飽和カルボン酸および／又はその誘導体（Ｂ）とは、不飽和カルボン酸、その無水物またはそれらの誘導体であり、１分子内にエチレン性不飽和結合とカルボキシル基、酸無水物基または誘導体基とを有する化合物である。不飽和カルボン酸類（Ｂ）の具体例としては、アクリル酸、メタクリル酸、α-エチルアクリル酸、マレイン酸、フマール酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、エンドシス−ビシクロ［２．２．１］ヘプト−２，３−ジカルボン酸（ナジック酸、商標）、メチル−エンドシス−ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボン酸（メチルナジック酸、商標）等の不飽和カルボン酸；これらの不飽和カルボン酸の無水物；不飽和カルボン酸ハライド、不飽和カルボン酸アミド、および不飽和カルボン酸イミドの誘導体などがあげられる。より具体的には、塩化マレニル、マレイミド、Ｎ−フェニルマレイミド、無水マレイン酸、無水イタコン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、グリシジルマレエートなどをあげることができる。これらの中では、アクリル酸、メタクリル酸、マレイン酸、ナジック酸、無水マレイン酸、無水イタコン酸、無水ナジック酸が好ましく、特に無水マレイン酸が好ましい。このような不飽和カルボン酸やその誘導体（Ｂ）は１種単独で使用することもできるし、２種以上を組み合せて使用することもできる。 The unsaturated carboxylic acid and / or derivative thereof (B) used in the present invention is an unsaturated carboxylic acid, an anhydride thereof or a derivative thereof, and an ethylenically unsaturated bond and a carboxyl group, acid anhydride in one molecule. A compound having a physical group or a derivative group. Specific examples of the unsaturated carboxylic acids (B) include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotone. Acid, endocis-bicyclo [2.2.1] hept-2,3-dicarboxylic acid (Nadic acid, trademark), methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid Examples thereof include unsaturated carboxylic acids such as acids (methylnadic acid, trademark); anhydrides of these unsaturated carboxylic acids; unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, and derivatives of unsaturated carboxylic acid imides. More specifically, maleyl chloride, maleimide, N-phenylmaleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like can be mentioned. Among these, acrylic acid, methacrylic acid, maleic acid, nadic acid, maleic anhydride, itaconic anhydride and nadic anhydride are preferable, and maleic anhydride is particularly preferable. Such unsaturated carboxylic acids and derivatives thereof (B) can be used alone or in combination of two or more.
本発明で使用する、（Ｂ）成分と異なる不飽和結合含有のラジカル反応性モノマー（Ｃ）は、ラジカル反応性を有する炭素−炭素二重結合、あるいは炭素−炭素三重結合の不飽和結合を有する化合物であれば制限なく使用できる。（Ｂ）成分単独、例えば無水マレイン酸単独でポリプロピレン樹脂の変性を行った場合、変性時に発生する無水マレイン酸ラジカルのポリプロピレン樹脂への連鎖移動反応が発生するため、変性ポリプロピレン樹脂の極端な分子量の低下が起こり、かつ未グラフトの無水マレイン酸が多く発生する。本発明で使用する不飽和結合含有のラジカル反応性モノマー（Ｃ）は、このような無水マレイン酸の連鎖移動反応を抑制するため配合する。（Ｃ）成分を配合することにより、変性ポリプロピレン樹脂の分子量の低下、および未グラフト成分の生成を抑制でき、かつグラフト量を上げることができる。使用する（Ｃ）成分として具体的には、（メタ）アクリル酸エステル系モノマー、アクリルアミド系モノマー、アクロニトリル、スチレン系モノマー、ハロゲン化ビニル系モノマー、ビニルエステル系モノマー、ビニルピリジン系モノマーなどがあげられ、これらの中では（メタ）アクリル酸エステル系モノマーが好ましい。 The radical reactive monomer (C) containing an unsaturated bond different from the component (B) used in the present invention has a carbon-carbon double bond having a radical reactivity or an unsaturated bond of a carbon-carbon triple bond. Any compound can be used without limitation. When the polypropylene resin is modified with the component (B) alone, for example, maleic anhydride alone, a chain transfer reaction of the maleic anhydride radical generated at the time of modification to the polypropylene resin occurs. A decrease occurs and a large amount of ungrafted maleic anhydride is generated. The unsaturated bond-containing radical reactive monomer (C) used in the present invention is blended in order to suppress such a chain transfer reaction of maleic anhydride. By mix | blending (C) component, the fall of the molecular weight of a modified polypropylene resin and the production | generation of an ungrafted component can be suppressed, and the graft amount can be raised. Specific examples of the component (C) to be used include (meth) acrylate monomers, acrylamide monomers, acrylonitrile, styrene monomers, vinyl halide monomers, vinyl ester monomers, vinyl pyridine monomers, and the like. Of these, (meth) acrylic acid ester monomers are preferred.
（Ｂ）成分と異なる不飽和結合含有のラジカル反応性モノマー（Ｃ）として用いる（メタ）アクリル酸エステル系モノマーの具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、 (メタ)アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸イコシル、（メタ）アクリル酸コシル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ジエチレングリコール、（メタ）アクリル酸グリセリンなどがあげることができる。いずれの（メタ）アクリル酸エステルを用いた場合も、変性ポリプロピレン樹脂の分子量低下の抑制効果は認められるが、その効果は配合量によって決まる。そのため、エステル部の炭素数が多い場合（具体的にはエステル部の炭素数が８以上）、つまり（メタ）アクリル酸エステルの分子量が大きくなる場合、所定の効果を得るための重量部見合いの配合量は多くなる。ポリプロピレン樹脂のような非極性樹脂を用いて溶融変性を行う場合、このような極性液状成分を多量に添加すると、混合物の性状が悪化し、生産時に押出機のホッパー下でブリッジング等の問題が起こり、生産上の支障をきたす。そのため、添加量を極力少なくするには、（C）成分としては、エステル部の炭素数が７以下の（メタ）アクリル酸エステルが望ましい。具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ジエチレングリコール、（メタ）アクリル酸グリセリン等が好ましく、特に、メタアクリル酸メチル、メタアクリル酸エチル、メタアクリル酸プロピル、メタアクリル酸ブチル、メタアクリル酸ヘキシル、メタアクリル酸ペンチル、メタアクリル酸ヘキシル、メタアクリル酸シクロヘキシル、メタアクリル酸ベンジルが好ましい。 Specific examples of the (meth) acrylate monomer used as the radical reactive monomer (C) containing an unsaturated bond different from the component (B) include methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) Lauryl acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, (meta ) Stearyl acrylate, Tridecyl (meth) acrylate, Tet (meth) acrylate Decyl, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, cosyl (meth) acrylate , Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diethylene glycol (meth) acrylate, glycerin (meth) acrylate, and the like. When any (meth) acrylic acid ester is used, the effect of suppressing the molecular weight reduction of the modified polypropylene resin is recognized, but the effect depends on the blending amount. Therefore, when the number of carbons in the ester part is large (specifically, the number of carbons in the ester part is 8 or more), that is, when the molecular weight of the (meth) acrylic acid ester is large, The blending amount increases. When melt-modifying using a nonpolar resin such as polypropylene resin, the addition of a large amount of such polar liquid components deteriorates the properties of the mixture and causes problems such as bridging under the hopper of the extruder during production. Occurs and causes production problems. Therefore, in order to reduce the addition amount as much as possible, the (C) component is preferably a (meth) acrylic acid ester having an ester moiety having 7 or less carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diethylene glycol (meth) acrylate, ( Preferred are glyceryl acrylate and the like, and in particular, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate. , Methacrylic Benzyl is preferred.
本発明で使用するラジカル開始剤（Ｄ）としては有機過酸化物などの公知のラジカル開始剤が制限なく使用できる。具体的には、１，１−ビス（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルペルオキシ）オクタン、ｎ−ブチル−４，４−ビス（ｔ−ブチルペルオキシ）バラレート、２，２−ビス（ｔ−ブチルペルオキシ）ブタン等のペルオキシケタール類；ジ−ｔ−ブチルペルオキシド、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、α，α′−ビス（ｔ−ブチルペルオキシ）ジイソプロピルベンゼン、２，５−ジメチル−２，５−ビス（ｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ビス（ｔ−ブチルペルオキシ）ヘキシン−３等のジアルキルペルオキシド類；アセチルペルオキシド、イソブチルペルオキシド、オクタノイルペルオキシド、デカノイルペルオキシド、ラウロイルペルオキシド、３，５，５−トリメチルヘキサノイルペルオキシド、ベンゾイルペルオキシド、２，５−ジクロロベンゾイルペルオキシド、ｍ−トリオイルペルオキシド等のジアシルペルオキシド類；ｔ−ブチルオキシアセテート、ｔ−ブチルペルオキシイソブチレート、ｔ−ブチルペルオキシ−２−エチルヘキサノエート、ｔ−ブチルペルオキシラウリレート、ｔ−ブチルペルオキシベンゾエート、ジ−ｔ−ブチルペルオキシイソフタレート、２，５−ジメチル−２，５−ビス（ベンゾイルペルオキシ）ヘキサン、ｔ−ブチルペルオキシマレイックアシッド、ｔ−ブチルペルオキシイソプロピルカーボネート、クミルペルオキシオクテート等のペルオキシエステル類；ジ（２−エチルヘキシル）ペルオキシジカーボネート、ジ（３−メチル−３−メトキシブチル）ペルオキシジカーボネート等のペルオキシジカーボネート類；ｔ−ブチルハイドロペルオキシド、クメンハイドロペルオキシド、ジイソプロピルベンゼンハイドロペルオキシド、２，５−ジメチルヘキサン−２，５−ジハイドロペルオキシド、１，１，３，３−テトラメチルブチルハイドロペルオキシド等のハイドロペルオキシド類などをあげることができる。これらの中ではベンゾイルペルオキシド、ｍ−トリオイルペルオキシド、ｔ−ブチルペルオキシ−２−エチルヘキサノエート、ジクミルペルオキシド、２，５−ジメチル−２，５−ビス（ｔ−ブチルペルオキシ）ヘキサン、ｔ−ブチルペルオキシベンゾエートなどが好ましい。これらは１種単独で、あるいは二種以上組み合わせて用いることができる。 As the radical initiator (D) used in the present invention, known radical initiators such as organic peroxides can be used without limitation. Specifically, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) Peroxyketals such as octane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; di-t-butyl peroxide, dicumyl peroxide, t- Butylcumyl peroxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis Dialkyl peroxides such as (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyl peroxide, octa Diacyl peroxides such as noyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,5-dichlorobenzoyl peroxide, m-trioyl peroxide; t-butyloxyacetate, t -Butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5 Peroxyesters such as bis (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbonate, cumylperoxyoctate; (Ruhexyl) peroxydicarbonate, peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2 , 5-dihydroperoxide, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Among these, benzoyl peroxide, m-trioyl peroxide, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t- Butyl peroxybenzoate is preferred. These can be used alone or in combination of two or more.
本発明の樹脂組成物における各成分の含有割合は、（Ａ）成分１００重量部、（Ｂ）成分０．１〜１０重量部、（Ｃ）成分０．１〜１０重量部、（Ｄ）成分０．０１〜１０重量部であって、好ましくは（Ａ）成分１００重量部、（Ｂ）成分０．５〜５重量部、（Ｃ）成分０．５〜５重量部、（Ｄ）０．１〜５重量部である。 The content ratio of each component in the resin composition of the present invention is as follows: (A) component 100 parts by weight, (B) component 0.1 to 10 parts by weight, (C) component 0.1 to 10 parts by weight, (D) component a 0.01-10 by weight unit, preferably 100 weight parts component (a), (B) component 0.5 to 5 parts by weight, (C) component 0.5 to 5 parts by weight, (D) 0 .1 to 5 parts by weight.
（Ｂ）成分０．１〜１０重量部、（Ｃ）成分０．１〜１０重量部、（Ｄ）成分０．０１〜１０重量部であるので、変性プロピレン樹脂の分子量を極端に低下させることなく高グラフト化することができる。 Component (B) 0.1 to 10 parts by weight lowers the component (C) 0.1 to 10 parts by weight, (D) are the components 0.01-10 by weight unit, the molecular weight of the modified propylene resin extremely High grafting can be achieved without any problems.
上記のようにして得られた変性ポリプロピレン樹脂の１３５℃デカリン中で測定される固有粘度［η］を［η］MPP（ｄｌ／ｇ）、ポリプロピレン樹脂（Ａ）の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＰＰ）（℃）、および変性ポリプロピレン樹脂の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＭＰＰ）（℃）、変性ポリプロピレン樹脂中に占める、不飽和カルボン酸および／またはその誘導体のグラフト量をＭＧ（重量％）、および（Ｂ）成分と異なる不飽和結合含有のラジカル反応性モノマー（Ｃ）のグラフト量をＥＧ（重量％）とした場合に、下記関係式（i）、（ii）、（iii）および(iv)を満足することを特徴とする変性ポリプロピレン樹脂。 The intrinsic viscosity [η] measured in decalin at 135 ° C. of the modified polypropylene resin obtained as described above is [η] MPP (dl / g), a differential scanning calorimeter (DSC) of the polypropylene resin (A). Tm (PP) (° C.) for the melting point to be measured, and Tm (MPP) (° C.) for the melting point to be measured by the differential scanning calorimeter (DSC) of the modified polypropylene resin, unsaturated carboxylic acid occupying in the modified polypropylene resin When the graft amount of the radical reactive monomer (C) containing an unsaturated bond different from the component (B) is EG (wt%), the following relationship is established: A modified polypropylene resin characterized by satisfying the formulas (i), (ii), (iii) and (iv).
０．７≦［η］MPP ≦ ２．０ ・・・（i）
０≦Ｔｍ（ＰＰ）−Ｔｍ（ＭＰＰ）≦１５ ・・・（ii）
０．８≦ＭＧ≦５ ・・・（iii）
０＜ＥＧ／ＭＧ ≦１ ・・・（iv）
0.7 ≦ [η] MPP ≦ 2.0 (i)
0 ≦ Tm (PP) −Tm (MPP) ≦ 15 (ii)
0.8 ≦ MG ≦ 5 (iii)
0 <EG / MG ≦ 1 (iv)
上記のようにして得られた変性ポリプロピレン樹脂の１３５℃デカリン中で測定される固有粘度［η］は、通常０．７〜２．０ ｄｌ／ｇ、好ましくは０．８〜２．０ ｄｌ／ｇの範囲内にあるのが望ましい。また変性に使用したポリプロピレン樹脂の融点（Ｔｍ（ＰＰ））と変性ポリプロピレン樹脂の融点（Ｔｍ（ＭＰＰ））の差は、通常０〜１５℃、好ましくは０〜１０℃の範囲内であるのが望ましい。一般的にポリプロピレン樹脂にラジカル開始剤を作用させて、不飽和結合を有するラジカル反応性モノマーをグラフト重合させる場合、モノマーのグラフトと同時にラジカル発生によるポリプロピレン樹脂の分子量、および融点の低下が起こる。この際、発生したポリマーラジカル、または／およびモノマーラジカルをいかに効率的に付加させるか、つまりグラフト結合したモノマーの量（グラフト量）が同一でより高分子量、かつ高融点の変性ポリプロピレン樹脂を得るかが課題となる。所定のグラフト量を得ることができても過度に分子量が低下、および／または融点が過度に低下した場合、具体的には固有粘度［η］が０．７ｄｌ／ｇ未満、および／または変性に使用したポリプロピレン樹脂の融点と変性ポリプロピレン樹脂の融点の差が１５℃以上になると、そのポリプロピレン樹脂が本来有している機械特性が発現しない。 The intrinsic viscosity [η] measured in 135 ° C. decalin of the modified polypropylene resin obtained as described above is usually 0.7 to 2.0 dl / g, preferably 0.8 to 2.0 dl / g. It is desirable to be within the range of g. The difference between the melting point (Tm (PP)) of the polypropylene resin used for modification and the melting point (Tm (MPP)) of the modified polypropylene resin is usually in the range of 0 to 15 ° C, preferably 0 to 10 ° C. desirable. In general, when a radical initiator is allowed to act on a polypropylene resin to graft polymerize a radical reactive monomer having an unsaturated bond, the molecular weight and melting point of the polypropylene resin are lowered due to radical generation simultaneously with the grafting of the monomer. At this time, how efficiently the generated polymer radicals and / or monomer radicals are added, that is, how to obtain a modified polypropylene resin having the same amount of grafted monomers (graft amount), higher molecular weight, and high melting point. Is an issue. If the molecular weight is excessively decreased and / or the melting point is excessively decreased even if a predetermined graft amount can be obtained, the intrinsic viscosity [η] is less than 0.7 dl / g, and / or When the difference between the melting point of the used polypropylene resin and the melting point of the modified polypropylene resin is 15 ° C. or more, the mechanical properties inherent to the polypropylene resin are not exhibited.
また、本発明の変性ポリプロピレン樹脂において、不飽和カルボン酸および／またはその誘導体（Ｂ）のグラフト量をＭＧ（重量％）とした場合、ＭＧは、０．８≦ＭＧ≦５、好ましくは１≦ＭＧ≦５である。ＭＧが１未満であれば、グラフト量が少ないため、所定の密着や接着性能が得られない。ＭＧが５を超えるとポリプロピレン樹脂との相溶性が低下し、逆に密着や接着性能が低下してしまう。 In the modified polypropylene resin of the present invention, when the graft amount of the unsaturated carboxylic acid and / or derivative (B) is MG (% by weight), MG is 0.8 ≦ MG ≦ 5, preferably 1 ≦ MG ≦ 5. If MG is less than 1, the amount of grafting is small, so that predetermined adhesion and adhesion performance cannot be obtained. When MG exceeds 5, compatibility with a polypropylene resin is lowered, and conversely, adhesion and adhesion performance are lowered.
更に、本発明の変性ポリプロピレン樹脂においては、不飽和カルボン酸および／またはその誘導体（Ｂ）のグラフト量をＭＧ（重量％）、（Ｂ）成分と異なる不飽和結合含有するラジカル反応性モノマー（Ｃ）のグラフト量をＥＧ（重量％）とした場合に、ＥＧ／ＭＧは０＜（ＥＧ／ＭＧ）≦１、好ましくは０．１≦（ＥＧ／ＭＧ）≦０．７５である。（ＥＧ／ＭＧ）＞１の場合、つまりＥＧがＭＧよりも多くなると、ポリプロピレン樹脂との相溶性が低下し、逆に密着や接着性能が低下してしまうため、好ましくない。 Furthermore, in the modified polypropylene resin of the present invention, the radical reactive monomer (C) containing an unsaturated bond different from the component (B) in which the graft amount of the unsaturated carboxylic acid and / or its derivative (B) is MG (wt%). ) Is defined as EG (% by weight), EG / MG satisfies 0 <(EG / MG) ≦ 1, preferably 0.1 ≦ (EG / MG) ≦ 0.75. In the case of (EG / MG)> 1, that is, when EG is larger than MG, compatibility with polypropylene resin is lowered, and conversely, adhesion and adhesion performance are lowered, which is not preferable.
本発明の変性ポリプロピレン樹脂は、上記関係式（i）、（ii）、（iii）、及び（iv）を満足するため、ポリプロピレン本来の特性を保持しつつ、従来からのポリプロピレン樹脂の欠点であった塗料や接着剤との密着性を改善し、かつ極性樹脂との複合化においても相溶性を改善したポリプロピレン樹脂組成物を得ることができる。更にこの変性ポリプロピレン樹脂は単独でも使用できるし、改質材としても使用できる。 The modified polypropylene resin of the present invention satisfies the above-mentioned relational expressions (i), (ii), (iii), and (iv), and thus is a drawback of conventional polypropylene resins while maintaining the original properties of polypropylene. Thus, a polypropylene resin composition having improved compatibility with paints and adhesives, and improved compatibility even in combination with a polar resin can be obtained. Furthermore, this modified polypropylene resin can be used alone or as a modifier.
本発明での製造法としては、樹脂同士あるいは樹脂と固体もしくは液体の添加物を混合するための公知の各種方法が採用可能である。好ましい例としては、各成分の全部もしくはいくつかを組み合わせて別々にヘンシェルミキサー、リボンブレンダー、ブレンダー等により混合して均一な混合物とした後、該混合物を混練する等の方法を挙げることができる。混練の手段としては、バンバリーミキサー、プラストミル、ブラベンダープラストグラフ、一軸又は二軸の押出機等の従来公知の混練手段が広く採用可能である。混練機の混練を行う場合の温度は（例えば、押出機ならシリンダー温度）、１００〜３００℃、好ましくは１６０〜２５０℃である。温度が低すぎるとグラフト量が向上しない場合があり、また、温度が高すぎると樹脂の分解が起こる場合がある。また、未グラフト成分を除去するため、真空ベント装置を設けた混練機を使用することが好ましい。 As the production method in the present invention, various known methods for mixing resins or resins and solid or liquid additives can be employed. Preferable examples include a method in which all or some of the components are combined and mixed separately with a Henschel mixer, a ribbon blender, a blender or the like to form a uniform mixture, and then the mixture is kneaded. As kneading means, conventionally known kneading means such as Banbury mixer, plast mill, Brabender plastograph, uniaxial or biaxial extruder can be widely employed. The temperature at which the kneader is kneaded (for example, the cylinder temperature for an extruder) is 100 to 300 ° C, preferably 160 to 250 ° C. If the temperature is too low, the graft amount may not be improved, and if the temperature is too high, decomposition of the resin may occur. In order to remove ungrafted components, it is preferable to use a kneader equipped with a vacuum vent device.
本発明に係る変性ポリプロピレン樹脂は、各種添加剤としてたとえばフェノール系、イオウ系、リン系などの酸化防止剤、滑剤、帯電防止剤、分散剤、銅害防止剤、中和剤、発泡剤、可塑剤、気泡防止剤、難燃剤、架橋剤、紫外線吸収剤、耐光安定剤などを含有していてもよい。 The modified polypropylene resin according to the present invention includes, as various additives, for example, phenol-based, sulfur-based, phosphorus-based antioxidants, lubricants, antistatic agents, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers. An agent, an anti-bubble agent, a flame retardant, a crosslinking agent, an ultraviolet absorber, a light stabilizer, and the like may be contained.
本発明に係る変性ポリプロピレン樹脂は、未変性のポリオレフィン樹脂、ポリアミド樹脂、ＡＢＳ樹脂などの極性樹脂、オレフィン系エラストマー、スチレン系エラストマーなどの熱可塑性エラストマー、タルク、モスハイジ、ガラスファイバー、カーボンブラックなどの充填材等と混合し、改質材として使用してもよい。 The modified polypropylene resin according to the present invention is filled with unmodified polyolefin resin, polyamide resin, ABS resin or other polar resin, olefin elastomer, thermoplastic elastomer such as styrene elastomer, talc, moss heidi, glass fiber, carbon black, etc. You may mix with materials etc. and use as a modifier.
以下本発明の実施例について説明する。
製造例１（ポリプロピレンＡ−１の重合）内容量３０００Ｌの攪拌機付きベッセル重合器に、ヘプタン１２２２Ｌ、トリエチルアルミニウム１４４ｇ、ジシクロペンチルジメトキシシラン２８８ｇ、ヘプタンでスラリー化したプロピレン重合用固体状チタン触媒成分５５ｇを装入した。重合槽内の窒素ガスを真空ポンプで除去し、プロピレンを装入し、昇温を開始した。重合温度７０℃で、重合圧力０．４３ MPa/Gに保つようにプロピレンを連続装入し、６時間重合を行った。重合終了後、メタノール１５１ｍＬ装入し、重合を終了させた。 得られたスラリーの固液分離を行い、得られたプロピレン共重合体を７０℃で真空乾燥し、プロピレン重合体６００ｋｇを得た。得られたポリプロピレン重合体の［η］は７．５ｄｌ／ｇ、融点は１６０℃であった。
Examples of the present invention will be described below.
Production Example 1 (Polymerization of Polypropylene A-1) Into a vessel polymerization vessel with an internal volume of 3000 L with stirrer, 122 g of heptane, 144 g of triethylaluminum, 288 g of dicyclopentyldimethoxysilane, 55 g of solid titanium catalyst component for propylene polymerization slurried with heptane I was charged. Nitrogen gas in the polymerization tank was removed with a vacuum pump, propylene was charged, and temperature increase was started. Propylene was continuously charged at a polymerization temperature of 70 ° C. so as to maintain a polymerization pressure of 0.43 MPa / G, and polymerization was carried out for 6 hours. After completion of the polymerization, 151 mL of methanol was charged to complete the polymerization. The obtained slurry was subjected to solid-liquid separation, and the resulting propylene copolymer was vacuum dried at 70 ° C. to obtain 600 kg of a propylene polymer. [Η] of the obtained polypropylene polymer was 7.5 dl / g, and the melting point was 160 ° C.
製造例１で得たＡ−１を１００重量部に、無水マレイン酸（Ｂ）（和光純薬（株）製、試薬）３重量部、メタクリル酸メチル（Ｃ−１）（和光純薬（株）製、試薬）０．５重量部、ｔ−ブチルパーオキシベンゾエート（Ｄ）（日本油脂（株）製、商標：パーブチルＺ）１重量部をヘンシェルミキサーで均一に混合した後、同方向二軸混練機（テクノベル（株）製、商標：ＫＺＷ３１−３０ＨＧ）にて２１０℃で加熱混練し、変性ポリプロピレン樹脂を得た。 100 parts by weight of A-1 obtained in Production Example 1, 3 parts by weight of maleic anhydride (B) (manufactured by Wako Pure Chemical Industries, Ltd., reagent), methyl methacrylate (C-1) (Wako Pure Chemical Industries, Ltd.) ), Reagent) 0.5 part by weight, 1 part by weight of t-butyl peroxybenzoate (D) (Nippon Yushi Co., Ltd., trademark: Perbutyl Z) was mixed uniformly with a Henschel mixer, A modified polypropylene resin was obtained by kneading at 210 ° C. with a kneading machine (trade name: KZW31-30HG, manufactured by Technobel Corp.).
Ｃ−１を３重量部に変更した以外は、実施例１と同じ方法で変性ポリプロピレン樹脂を得た。 A modified polypropylene resin was obtained in the same manner as in Example 1 except that C-1 was changed to 3 parts by weight.
Ｃ成分をメタクリル酸ベンジル（Ｃ−２）（和光純薬（株）製、試薬）１．５重量部に変更した以外は、実施例１と同じ方法で変性ポリプロピレン樹脂を得た。 A modified polypropylene resin was obtained in the same manner as in Example 1 except that C component was changed to 1.5 parts by weight of benzyl methacrylate (C-2) (manufactured by Wako Pure Chemical Industries, Ltd., reagent).
[比較例１]
（Ｃ）成分を使用しなかった以外は、実施例１と同じ方法で変性ポリプロピレン樹脂を得た。
[Comparative Example 1]
A modified polypropylene resin was obtained in the same manner as in Example 1 except that the component (C) was not used.
[比較例２]
（Ｃ）成分を使用せず、ｔ−ブチルパーオキシベンゾエート（Ｄ）（日本油脂（株）製、商標：パーブチルＺ）３重量部にしたこと以外は、実施例１と同じ方法で変性ポリプロピレン樹脂を得た。
[Comparative Example 2]
(C) Modified polypropylene resin by the same method as Example 1 except having used 3 parts by weight of t-butyl peroxybenzoate (D) (trade name: Perbutyl Z, manufactured by NOF Corporation) without using the component. Got.
本発明の変性ポリプロピレン樹脂は、自動車、家電等の工業部品分野；フィルム、シート等の包装分野；その他容器分野、繊維分野などの分野において幅広く使用することができる。 The modified polypropylene resin of the present invention can be widely used in the fields of industrial parts such as automobiles and home appliances; the field of packaging of films and sheets; the field of containers and the field of textiles.
Claims (2)
ｇ）、ポリプロピレン樹脂（Ａ）の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＰＰ）（℃）、および変性ポリプロピレン樹脂の示差走査熱量計（ＤＳＣ）で測定される融点をＴｍ（ＭＰＰ）（℃）、無水マレイン酸（Ｂ）のグラフト量をＭＧ（重量％）、およびエステル部の炭素数が７以下の（メタ）アクリル酸エステル（Ｃ）のグラフト量をＥＧ（重量％）とした場合に、下記関係式（i）、（ii）、（iii）および(iv)を満足することを特徴とする変性ポリプロピレン樹脂。
０．７≦［η］MPP ≦ ２．０ ・・・（i）
０≦Ｔｍ（ＰＰ）−Ｔｍ（ＭＰＰ）≦１５ ・・・（ii）
０．８≦ＭＧ≦５ ・・・（iii）
０＜ＥＧ／ＭＧ ≦１ ・・・（iv） 0.1 to 10 parts by weight of maleic anhydride (B) and 0.5 to 5 parts by weight of (meth) acrylic acid ester (C) having 7 or less carbon atoms in the ester part with respect to 100 parts by weight of the polypropylene resin (A) And a modified polypropylene resin modified with 0.01 to 10 parts by weight of a radical initiator (D), wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is [η] MPP (dl /
g) The melting point of the polypropylene resin (A) measured with a differential scanning calorimeter (DSC) is Tm (PP) (° C.), and the melting point of the modified polypropylene resin is measured with a differential scanning calorimeter (DSC) of Tm ( MPP) (° C.), the graft amount of maleic anhydride (B) is MG (% by weight), and the graft amount of (meth) acrylic acid ester (C) having an ester part of 7 or less carbon atoms is EG (% by weight) A modified polypropylene resin characterized by satisfying the following relational expressions (i), (ii), (iii) and (iv):
0.7 ≦ [η] MPP ≦ 2.0 (i)
0 ≦ Tm (PP) −Tm (MPP) ≦ 15 (ii)
0.8 ≦ MG ≦ 5 (iii)
0 <EG / MG ≦ 1 (iv)
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