JPH03239710A - Production of modified polymer - Google Patents
Production of modified polymerInfo
- Publication number
- JPH03239710A JPH03239710A JP3580790A JP3580790A JPH03239710A JP H03239710 A JPH03239710 A JP H03239710A JP 3580790 A JP3580790 A JP 3580790A JP 3580790 A JP3580790 A JP 3580790A JP H03239710 A JPH03239710 A JP H03239710A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- carboxylic acid
- unsaturated carboxylic
- acid
- derivative
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920000098 polyolefin Polymers 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002904 solvent Substances 0.000 claims description 16
- 238000010559 graft polymerization reaction Methods 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 7
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 150000001451 organic peroxides Chemical class 0.000 abstract description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 abstract 1
- -1 ethylene, propylene Chemical group 0.000 description 25
- 239000000203 mixture Substances 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 10
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- VFIBREUMBSEBTH-MDZDMXLPSA-N 3-[(1E)-deca-1,9-dienyl]oxolane-2,5-dione Chemical compound C=CCCCCCC\C=C\C1CC(=O)OC1=O VFIBREUMBSEBTH-MDZDMXLPSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 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 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920006112 polar polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-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
- LVYLCBNXHHHPSB-UHFFFAOYSA-N 2-hydroxyethyl salicylate Chemical compound OCCOC(=O)C1=CC=CC=C1O LVYLCBNXHHHPSB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical class ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- BIUMPKSWMFBEOF-UHFFFAOYSA-N (4-nonylphenyl) dihydrogen phosphate Chemical compound CCCCCCCCCC1=CC=C(OP(O)(O)=O)C=C1 BIUMPKSWMFBEOF-UHFFFAOYSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- SAUIEQQGRRLFRA-UHFFFAOYSA-N 1,1-dibromo-2,2-dichloropropane Chemical compound BrC(C(C)(Cl)Cl)Br SAUIEQQGRRLFRA-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- IWGFWLBRRGRWAO-UHFFFAOYSA-N 1-chlorosulfonyloxydodecane Chemical compound CCCCCCCCCCCCOS(Cl)(=O)=O IWGFWLBRRGRWAO-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- LSRGVBOHVMLGKY-UHFFFAOYSA-N 2,3-dimethyl-5,6-dinitrosobenzene-1,4-dicarboxamide Chemical compound CC1=C(C)C(C(N)=O)=C(N=O)C(N=O)=C1C(N)=O LSRGVBOHVMLGKY-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- HVYJSOSGTDINLW-UHFFFAOYSA-N 2-[dimethyl(octadecyl)azaniumyl]acetate Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CC([O-])=O HVYJSOSGTDINLW-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- JXOFJGPILYVSMN-UHFFFAOYSA-N 2-hydroxy-4-octylbenzoic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C(O)=C1 JXOFJGPILYVSMN-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-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
- 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
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
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- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野］
本発明はポリオレフィンのグラフト重合による新規変性
重合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a novel modified polymer by graft polymerization of polyolefins.
該変性重合体は、そのまま、または該変性重合体とポリ
オレフィンとをブレンドした変性重合体組成物の形で、
あるいはポリオレフィン、他の機能を有する酸素バリヤ
ー性樹脂、金属板または箔１紙等とラミネートして、多
層フィルムの補強層または接着層として使用することが
でき１食品包装材、産業包装材、自動車業界等において
利用されるものである。The modified polymer may be used as it is or in the form of a modified polymer composition obtained by blending the modified polymer and a polyolefin.
Alternatively, it can be laminated with polyolefin, oxygen barrier resin with other functions, metal plate or foil paper, etc., and used as a reinforcing layer or adhesive layer of multilayer film.1 Food packaging material, industrial packaging material, automobile industry. It is used in such cases.
［従来の技術および課題］
ポリオレフィンは良好な機械的性質、成形性等を有して
いるが、反面、無極性であるため金属、ガラスおよび極
性樹脂への接着性が悪いという欠点がある。[Prior Art and Problems] Polyolefins have good mechanical properties, moldability, etc., but on the other hand, because they are nonpolar, they have the disadvantage of poor adhesion to metals, glass, and polar resins.
このような欠点を補うため、ポリオレフィンに、無溶媒
または溶媒を使用してもポリオレフィンが溶解、溶融し
ない状態でアクリル酸、無水マレイン酸、アクリル酸メ
チルなどの極性上ツマ−を単独クラフト重合する方法（
特開昭５Ｏ−７７４９３）や、無水マレイン酸、マレイ
ミド等の不飽和カルボン酸とプロピレン等のオレフィン
（特開昭６４−８７６１１）またはビニルトリメトキシ
シラン等の不飽和シラン化合物（特開平１−１０８２０
７）を共存させグラフト共重合させる方法が知られてい
るが、いずれら充分な接着性は得られていない。In order to compensate for these drawbacks, we have developed a method in which polar polymers such as acrylic acid, maleic anhydride, and methyl acrylate are monopolymerized into polyolefin without a solvent or in a state in which the polyolefin does not dissolve or melt even with the use of a solvent. (
Unsaturated carboxylic acids such as maleic anhydride and maleimide and olefins such as propylene (Japanese Patent Publication No. 64-87611) or unsaturated silane compounds such as vinyltrimethoxysilane (Japanese Patent Publication No. 1-10820)
7) is known to coexist and perform graft copolymerization, but none of these methods have been able to provide sufficient adhesion.
［課題を解決するための手段］
本発明者等は１以上の問題につき研究の結果、ポリオレ
フィンに無溶媒で、または溶媒を使用してもポリオレフ
ィンが溶解、溶融しない状態で、不飽和脂肪族カルボン
酸およびその誘導体と不飽和カルボン酸およびその誘導
体を共存させグラフト共重合させることにより、金属、
ガラス、極性樹脂に対する接着性が大きく向上した変性
重合体を発見し本発明に到達した。[Means for Solving the Problems] As a result of research on one or more problems, the present inventors have found that unsaturated aliphatic carbon atoms can be added to polyolefin without a solvent or in a state where the polyolefin does not dissolve or melt even when a solvent is used. Metals,
The present invention was achieved by discovering a modified polymer with greatly improved adhesion to glass and polar resins.
すなわち、ポリオレフィンの接着性を改善するために、
ポリオレフィンにラジカル開始剤を使用して式（ＩＣに
て示される化合物
をグラフト重合するにあたり、不飽和カルボン酸あるい
はその誘導体を共存させる変性重合体の製造法を提供す
るものである。更に、この場合において無溶媒または溶
媒を使用してもポリオレフィンが溶解または溶融しない
状態でグラフト共重合することにより、上記問題点を解
決することを見いだし本発明を完成するに到った。That is, to improve the adhesion of polyolefins,
The present invention provides a method for producing a modified polymer in which an unsaturated carboxylic acid or a derivative thereof coexists when graft polymerizing a compound represented by the formula (IC) using a radical initiator to a polyolefin. The present inventors have discovered that the above problems can be solved by graft copolymerizing the polyolefin in a state in which the polyolefin is not dissolved or melted even with or without a solvent, and has completed the present invention.
本発明にいう、ポリオレフィンとはエチレン、プロピレ
ン、ｌ−ブテン、１−ヘキセン、３−メチル−１−ペン
テン等のオレフィンの単独重合体またはこれらオレフィ
ンのランダムないしブロック共重合体もしくはこれらオ
レフィンを主成分とし、これに酢酸ビニル、アクリル酸
、メタクリル酸、アクリル酸アルキルエステル、メタク
リル酸アルキルエステル等を共重合させた共重合体を意
味する。In the present invention, polyolefin refers to a homopolymer of olefins such as ethylene, propylene, l-butene, 1-hexene, 3-methyl-1-pentene, or a random or block copolymer of these olefins, or a main component consisting of these olefins. It means a copolymer obtained by copolymerizing vinyl acetate, acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester, etc.
具体的には、例えば高密度ポリエチレン、低密度ポリエ
チレン、線状低密度ポリエチレン、ポリプロピレン、エ
チレン−プロピレンランダム共重合体、エチレン−プロ
ピレンゴム、エチレン−ブテン−１ゴム、エチレン−プ
ロピレン−１−ブテンランダム共重合体、エチレン−プ
ロピレンブロック共重合体、エチレン−プロピレン−４
−ブテンブロック共重合体、エチレン−酢酸ビニル共重
合体、プロピレン−１−ブテンランダム共重合体、エチ
レン−アクリル酸共重合体、エチレン−メタクリル酸共
重合体の金属塩、エチレン−メタクリル酸メチル共重合
体、エチレン−アクリル酸エチル共重合体等である。こ
れらは単独もしくは２種以上混合して用いてもよい。Specifically, for example, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene rubber, ethylene-butene-1 rubber, ethylene-propylene-1-butene random Copolymer, ethylene-propylene block copolymer, ethylene-propylene-4
-Butene block copolymer, ethylene-vinyl acetate copolymer, propylene-1-butene random copolymer, ethylene-acrylic acid copolymer, metal salt of ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer polymer, ethylene-ethyl acrylate copolymer, etc. These may be used alone or in combination of two or more.
ラジカル開始剤としては遊離基を発生する化合物、主と
して有機過酸化物を使用する。たとえば、ジし一ブチル
バーオキシド、ジクミルパーオキシド、ｔ−ブチルクミ
ルパーオキシド、等のジアルキルパーオキシド、アセチ
ルパーオキシド、ｉ−ブチリルパーオキシド、オクタノ
イルパーオキシド、ラウロイルパーオキシド、ベンゾイ
ルパーオキシド、０−メチルベンゾイルパーオキシド等
のジアシルパーオキシド、ジｉ−プロビルパー才キシジ
カーポネート、ジ２−エチルヘキシルパーオキシジカー
ボネート等のパーオキシジカーボネート、ｔ−ブチルパ
ーオキシビバレート、ｔ−ブチルパーオキシラウレート
等のパーオキシエステル、メチルエチルケトンパーオキ
シド、シクロヘキサノンパーオキシド等のケトンパーオ
キシド、１，１−ビスｔ−ブチルパーキシシクロヘキサ
ン、２．２−ビスｔ−ブチＩレバーオキシオクタン専の
パーオキシケタール、ｔ−ブチルハイドロパーオキシド
、クメンハイドロパーオキシド等のハイドロパーオキシ
ド、２．２−アゾビスイソブチロニトリル等のアゾ化合
物、酸素等が挙げられる。Compounds that generate free radicals, mainly organic peroxides, are used as radical initiators. For example, dialkyl peroxides such as di-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, i-butyryl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, Diacyl peroxide such as 0-methylbenzoyl peroxide, di-propylene peroxydicarbonate, peroxydicarbonate such as di-2-ethylhexyl peroxydicarbonate, t-butylperoxybivalate, t-butylperoxy Peroxy esters such as laurate, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, 1,1-bis t-butyl peroxycyclohexane, and peroxy ketals exclusively for 2,2-bis t-butyl liver oxyoctane. , t-butyl hydroperoxide, hydroperoxides such as cumene hydroperoxide, azo compounds such as 2,2-azobisisobutyronitrile, and oxygen.
ラジカル開始剤の使用量は通常ポリオレフィンに対し０
．００１〜３０重量％、好ましくは０００５〜２０重量
％である。The amount of radical initiator used is usually 0 for polyolefin.
．． 001 to 30% by weight, preferably 0005 to 20% by weight.
また、ポリオレフィンの改質を目的として使用する化合
物としては、
であるが、好ましくは一般式におけるＲ 、、 Ｒ、。In addition, the compounds used for the purpose of modifying polyolefins are as follows, but preferably R,, R, in the general formula.
Ｒ，、Ｒ，もしくはＲ，にコハク酸無水物を含む化合物
である。具体的には、１．９デカジエニル無水コハク酸
、アリル無水コハク酸、ｌ−オクテン−３−無水コハク
酸等が用いられる。A compound containing succinic anhydride in R, , R, or R. Specifically, 1.9 decadienyl succinic anhydride, allyl succinic anhydride, l-octene-3-succinic anhydride, etc. are used.
式（Ｉ）にて示される化合物の使用量は被着物の性質に
より目的とする変性重合体の性質等が影響をうけるので
特定した数値として言うことができないが１通常ポリオ
レフィンに対して０．１〜１００重量％である。The amount of the compound represented by formula (I) to be used cannot be stated as a specific value because the properties of the target modified polymer are affected by the properties of the adherend, but it is usually 0.1 to 1 polyolefin. ~100% by weight.
本発明で言う不飽和カルボン酸あるいはその誘導体とし
ては、無水マレイン酸、マレイン酸、マレイン酸ジアル
キルエステル及びＮ−アルキル。Examples of unsaturated carboxylic acids or derivatives thereof in the present invention include maleic anhydride, maleic acid, dialkyl maleate, and N-alkyl maleate.
フェニル置換マレイミド、マレイミド等が用いられる。Phenyl-substituted maleimide, maleimide, etc. are used.
好ましくは無水マレイン酸、マレイミドである。Preferred are maleic anhydride and maleimide.
不飽和カルボン酸あるいはその誘導体の使用量は、目的
とする変性重合体の性質等により異なり数的に言うこと
ができないが１通常ポリオレフィンに対して０．１〜１
００重量％であるが、好ましくは上記式（Ｉ）で示す化
合物の０．７〜１．５当量で反応させることが好ましい
。The amount of unsaturated carboxylic acid or its derivative to be used varies depending on the properties of the target modified polymer and cannot be expressed numerically, but it is usually 0.1 to 1 per polyolefin.
00% by weight, preferably 0.7 to 1.5 equivalents of the compound represented by the above formula (I).
グラフト反応方法は無溶媒または溶媒を使用し÷６ボリ
オレフインが溶解、溶融しない状態でグラフト重合する
方法が好ましい。The graft reaction method is preferably a method in which graft polymerization is carried out without a solvent or in a state in which ÷6 polyolefin is dissolved or not melted.
更に詳細に記載すれば、クラフト重合の温度はポリオレ
フィンが融解する温度より低い温度が好ましい。通常は
ポリオレフィンの融点のピーク温度より少なくとも２５
℃低い温度で行なう、また、クラフト重合の効率を上げ
るためには、該ピーク温度下１００℃からピーク温度下
２５℃の範囲内で行なうことが好ましい０反応時間は通
常０．５〜５時間程度である。More specifically, the temperature of the kraft polymerization is preferably lower than the temperature at which the polyolefin melts. Usually at least 25° below the peak melting temperature of the polyolefin.
The reaction time is usually about 0.5 to 5 hours.It is preferably carried out at a low temperature, and in order to increase the efficiency of kraft polymerization, it is preferably carried out within the range of 100 °C below the peak temperature to 25 °C below the peak temperature. It is.
使用するポリオレフィンの形状は、グラフト反応の効率
上フラン状態もしくは平均粒径が大きくと６７００μで
あることがグラフトの効率上好ましい。The shape of the polyolefin used is preferably a furan state or a large average particle size of 6700 μm in terms of efficiency of grafting reaction.
重合反応に要する時間は、実質的にラジカル開始剤が有
効に分解消費されるにふされしい温度と時間の条件を必
要とする。The time required for the polymerization reaction requires temperature and time conditions such that the radical initiator is effectively decomposed and consumed.
また、溶媒を使用するグラフト重合は連鎖移動性の低い
不活性溶媒を使用し、ポリオレフィンが溶解及び融解し
ない条件で行なうことが好ましい。Furthermore, it is preferable that the graft polymerization using a solvent be carried out using an inert solvent with low chain transfer properties and under conditions in which the polyolefin does not dissolve or melt.
このような溶媒を具体的に例示すれば、好ましい溶媒と
して、イソブタン、ベンクン、ヘキサン、シクロヘキサ
ン、オクタン等の飽和の炭化水素およびトルエン、キシ
レン等の芳香族炭化水素を挙げることができる。Specific examples of such solvents include saturated hydrocarbons such as isobutane, benzene, hexane, cyclohexane, and octane, and aromatic hydrocarbons such as toluene and xylene.
実質的に溶媒の存在しない系でグラフト重合を行なうこ
とは１本発明の目的である不飽和脂肪族カルボン酸化合
物あるいはその誘導体を高効率でクラフトするに適して
いる。Carrying out graft polymerization in a system substantially free of solvent is suitable for highly efficient crafting of unsaturated aliphatic carboxylic acid compounds or derivatives thereof, which is the object of the present invention.
反応器中に各試薬を仕込む際に付着する成分もしくはグ
ラフト反応時に飛散する成分を洗い流す等の目的で極少
量の溶媒を使用することは差し支えない。There is no problem in using a very small amount of solvent for purposes such as washing away components that adhere when charging each reagent into the reactor or components that scatter during the graft reaction.
ここで使用し得る溶媒としては１通常の溶媒を使用し得
るが、アセトン、メチルエチルケトン。As the solvent that can be used here, one common solvent can be used, such as acetone, methyl ethyl ketone.
トルエン、キシレン、テトラヒドロフラン等が好ましい
。Toluene, xylene, tetrahydrofuran and the like are preferred.
使用成分の添加順序はポリオレフィン、不飽和脂肪族カ
ルボン酸化合物あるいはその誘導体、不飽和カルボン酸
あるいはその誘導体、ラジカル開始剤等で、必要に応じ
て溶媒がグラフト重合時に同時に接触すればよく、特に
順序を問題にしない。The order of addition of the components used is polyolefin, unsaturated aliphatic carboxylic acid compound or its derivative, unsaturated carboxylic acid or its derivative, radical initiator, etc. If necessary, the solvent may be added at the same time during graft polymerization. is not an issue.
重合終了後、未反応の式（１）にて示される化合物、不
飽和カルボン酸あるいはその誘導体、ラジカル開始剤及
び反応副生物を除去するために南媒を使用して抽出６し
くは溶解再沈による洗浄をすることは可能である。After completion of the polymerization, extraction or dissolution-reprecipitation is performed using a southern solvent to remove the unreacted compound represented by formula (1), unsaturated carboxylic acid or its derivative, radical initiator, and reaction by-products. It is possible to wash with
ここで得た変性重合体もしくは該樹脂組成物はガラス、
金属、炭素繊維、無機繊維、！＃、機フィラー、ポリエ
チレンテレフタレート、ナイロン。The modified polymer or resin composition obtained here may be glass,
Metal, carbon fiber, inorganic fiber! #, machine filler, polyethylene terephthalate, nylon.
エチレン−酢酸ビニル共重合体の部分加水物（ＥＶＯＨ
Ｉ 、ポリエチレンカーボネート、ポリフェニレンオキ
シド、ポリオレフィン等の樹脂と複合しで使用すること
が可能である。Ethylene-vinyl acetate copolymer partial hydrate (EVOH)
It can be used in combination with resins such as I, polyethylene carbonate, polyphenylene oxide, and polyolefin.
また後で例示する周知の添加剤、配合剤を組成物の使用
目的に応じて配合してもよい。Further, well-known additives and compounding agents, which will be exemplified later, may be added depending on the intended use of the composition.
添加剤、配合剤の例を示せば、酸化防止剤（耐熱安定剤
）、紫外線吸収剤（光安定剤）、帯電防止剤、防曇剤、
ＩＩ燃剤、滑剤（スリップ剤、アンチブロッキング剤）
、無機および有機充填剤、補強材、着色剤（染料、顔料
）、発泡剤、架橋剤。Examples of additives and compounding agents include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents,
II Refueling agent, lubricant (slip agent, anti-blocking agent)
, inorganic and organic fillers, reinforcing materials, colorants (dyes, pigments), blowing agents, crosslinking agents.
香料等である。Flavors, etc.
耐熱安定剤の例を示せば、フェノ−！し系安定剤、硫黄
系安定剤、またはリン系安定剤等を挙げることができ、
具体的には、例えば２．６−ジｔ−ブチル−４−メチル
フェノール、ステアリル−〇−（３，５−ジ−ｔ−ブチ
ル−４−ヒドロキシフェニル）プロピオネート、１−（
４−ヒドロキシ−３，５−ジ−ｔ−ブチルアミノフェニ
ル）−３，５−ジオクチルチオ−２，４，６−トリアジ
ン、２．２゛−メチレンビス（４−メチル−６−ｔ−ブ
チルフェノール）、２．２°−メチレンビス（４−エチ
ル−６−ｔ−ブチルフェノール）、４．４’−チオビス
（３−メチル−６−ｔ−ブチルフェノール）、１．１．
３−）リス（２−メチル−４−ヒドロキシ−５−ｔ−ブ
チルフェニル）ブタン、１．３．５−１−リメチル−２
゜４．６−トリス（３，５−ジ−ｔ−ブチル４−ヒドロ
キシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシベンジル）イソシアヌレート、テ
トラキスＩメチレン−３（３°、５°−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオネートコメタン等
のフェノール系安定剤、ジラウリルチオジプロピオネー
ト、ジステアリルチオジプロピオネート、ペンタエリス
リトールテトララウリルチオプロビオネート等の硫黄系
安定剤、トリス（ノニルフェニル）ホスファイト、ジス
テアルリルベンタエリスリトールジホスファイト、テト
ラ（トリデシル）−１゜１．３−トリス（２−メチル−
５−ｔ−ブチル−４−ヒドロキシフェニル）ブタンジホ
スファイト、テトラキス（２，４−ジ−ｔ−ブチルフェ
ニル）４．４°−ビフェニレンジホスファイト。An example of a heat-resistant stabilizer is pheno! Examples include phosphorus-based stabilizers, sulfur-based stabilizers, and phosphorus-based stabilizers.
Specifically, for example, 2,6-di-t-butyl-4-methylphenol, stearyl-〇-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1-(
4-hydroxy-3,5-di-t-butylaminophenyl)-3,5-dioctylthio-2,4,6-triazine, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 2.2°-methylenebis(4-ethyl-6-t-butylphenol), 4.4'-thiobis(3-methyl-6-t-butylphenol), 1.1.
3-) Lis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1.3.5-1-limethyl-2
゜4.6-Tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tetrakis I methylene-3(3 phenolic stabilizers such as °,5°-di-t-butyl-4-hydroxyphenyl)propionate comethane, dilaurylthiodipropionate, distearylthiodipropionate, pentaerythritol tetralaurylthioprobionate, etc. Sulfur stabilizer, tris(nonylphenyl) phosphite, distearlylbentaerythritol diphosphite, tetra(tridecyl)-1゜1.3-tris(2-methyl-
5-t-butyl-4-hydroxyphenyl)butane diphosphite, tetrakis(2,4-di-t-butylphenyl)4.4°-biphenylene diphosphite.
９、ｌＯ−ジ−ヒドロ−９−オキサ−１Ｏ−ホスファフ
ェナンスレン−１０−オキサイド等の燐系安定剤を示し
得る。Phosphorous stabilizers such as 9,1O-di-hydro-9-oxa-1O-phosphaphenanthrene-10-oxide may be mentioned.
光安定剤としてはサリチル酸系、ベンゾフェノン系、ベ
ンゾトリアゾール系等を挙げることができ、具体的な例
示をすれば、フェニルサリチラート、ｐ−オクチルサリ
チラート、モノグリコールサリチラート、ｐ−ｔ−プチ
ルサリチラート等のサリチル酸系安定剤、２，４−ジヒ
ドロキシベンゾフェノン、２−ヒドロキシ−４−メトキ
シベンゾフェノン、２．２°−ジヒドロキシ−４−メト
キシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクチ
ルオキシベンゾフェノン、２−ヒドロキシ−４−オクタ
デシルオキシベンゾフェノン、２ヒドロキシ−４−ドデ
シルオキシベンゾフェノン等のベンゾフェノン系安定剤
、２− （２’ −ヒドロキシ−５°−メチルフェニル
）ベンゾトリアゾール、２−（２°−ヒドロキシ−４′
−ｎ−オクチルオキシフェニル）ベンゾトリアゾール等
のベンゾトリアゾール系安定剤、レゾルシノールモノベ
ンゾアート等を示し得る。Examples of light stabilizers include salicylic acid-based, benzophenone-based, benzotriazole-based, etc. Specific examples include phenyl salicylate, p-octylsalicylate, monoglycol salicylate, p-t - Salicylic acid stabilizers such as butyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2.2°-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxy Benzophenone stabilizers such as benzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2hydroxy-4-dodecyloxybenzophenone, 2-(2'-hydroxy-5°-methylphenyl)benzotriazole, 2-(2°- Hydroxy-4'
benzotriazole stabilizers such as -n-octyloxyphenyl)benzotriazole, resorcinol monobenzoate, and the like.
帯電防止剤、防曇剤としてはペンタエリスリットモノス
テアレート、グリセリンモノステアレート、グリセリン
ジステアレート、トリメチロールプロパンモノステアレ
ート、ソルビタンモノパルミテート、ポリエチレノグリ
コールモノステアレート等のエステル類、硫酸ラウリル
ソーダ、クロロスルホン酸ラウリル、硫酸化オレイン酸
、ドデシルベンゼンスルホン酸ソーダ等の硫酸化物、燐
酸モノオレイル、燐酸ジオレイル、燐酸モノラウリル、
燐酸ジラウリル、燐酸モノセチル、＃４ｒ！ａジセチル
、燐酸モノノニルフェニル、燐酸ジノニルフェニル等の
燐酸化物、Ｎ−メチル−Ｎ−酢酸ソーダオレイン酸アミ
ド、Ｎ、Ｎ−ジェタノールラウリン酸アミド等のアミド
類、ラウリルトリメチルアンモニウムクロライド、ラウ
リルジメチルベンジルアンモニウムクロライド、ラウリ
ルジェタノールメチルアンモニウムクロライド、ステア
リルトリメチルアンモニウムメトサルフェート等の第四
アンモニウム塩、ステアリルジメチルベタイン、ラウリ
ルジヒドロキシベタイン、ラウリルジメチルスルホベタ
イン等のベタイン類、ポリエチレングリコール型非イオ
ン帯電防止剤等を例示することができる。Antistatic agents and antifogging agents include esters such as pentaerythritol monostearate, glycerin monostearate, glycerin distearate, trimethylolpropane monostearate, sorbitan monopalmitate, polyethylene glycol monostearate, and sulfuric acid. Sulfates such as lauryl soda, lauryl chlorosulfonate, sulfated oleic acid, sodium dodecylbenzenesulfonate, monooleyl phosphate, dioleyl phosphate, monolauryl phosphate,
Dilauryl phosphate, monocetyl phosphate, #4r! Phosphate oxides such as dicetyl, monononylphenyl phosphate, dinonylphenyl phosphate, amides such as N-methyl-N-acetic acid soda oleic acid amide, N,N-jetanollauric acid amide, lauryl trimethylammonium chloride, lauryl dimethyl Quaternary ammonium salts such as benzyl ammonium chloride, lauryl jetanol methyl ammonium chloride, stearyl trimethyl ammonium methosulfate, betaines such as stearyl dimethyl betaine, lauryl dihydroxy betaine, lauryl dimethyl sulfobetaine, polyethylene glycol type nonionic antistatic agents, etc. I can give an example.
ＩＩＩ燃剤としては、塩素化パラフィン、塩素化ポリエ
チレン、無水クロレンチツク酸、四臭化ビスフェノール
Ａ、四臭化無水フタール酸、ジブロモジクロロプロパン
等のハロゲン系Ｎ燃剤、ト１１スクロロエチルホスフエ
ート、ビスクロロプロピルクロロエチルホスフェート、
リン酸エステＩし等の燐系難燃剤、酸化アンチモン、水
酸化マグネシウム等の非ハロゲン型難燃剤等を例示する
ことができる。III refractants include chlorinated paraffin, chlorinated polyethylene, chlorentic anhydride, tetrabrominated bisphenol A, tetrabrominated phthalic anhydride, dibromodichloropropane and other halogen-based N refractories, to-11-schloroethyl phosphate, bischloro propyl chloroethyl phosphate,
Examples include phosphorus-based flame retardants such as phosphate ester I, and non-halogen type flame retardants such as antimony oxide and magnesium hydroxide.
滑剤（広義にスリップ剤、アンチブロッキング剤等を含
む）としでは例えば炭化水素系として流動パラフィン、
天然パラフィン、マイクロワックス、合成ワックス、低
分子量ポリエチレン等を、脂肪酸系としてステアリン酸
等を、脂肪酸アミド系として脂肪酸アミド、アルキレン
ビス脂肪酸アミド等を、例えばステアリン酸アミド、バ
ルミチン酸アミド、メチレンビスステアリルアミド、エ
チレンビスステアリルアミド、オレイン酸アミド等を、
エステル系として脂肪酸の低級アルコールエステル、脂
肪酸の多価アルコールエステル、脂肪酸のポリグリコー
ルエステル等を、脂肪酸低級アルコールエステルとして
ステアリン酸ブチル等を、アルコール系として脂肪族ア
ルコール、多価アルコール、ポリグリコール等を、金属
石鹸等を挙げることができる。Examples of lubricants (including slip agents, anti-blocking agents, etc. in a broad sense) include hydrocarbons such as liquid paraffin,
Natural paraffin, microwax, synthetic wax, low molecular weight polyethylene, etc., fatty acid type such as stearic acid, fatty acid amide type such as fatty acid amide, alkylene bis fatty acid amide, etc., such as stearic acid amide, balmitic acid amide, methylene bis stearyl amide. , ethylene bisstearylamide, oleic acid amide, etc.
Ester types include lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, etc. Fatty acid lower alcohol esters include butyl stearate, etc. Alcohol types include aliphatic alcohols, polyhydric alcohols, polyglycols, etc. , metal soap, etc.
充填剤としては例えばカーボンブラック、ホワイトカー
ボン、炭酸カルシウム、含水塩基性炭酸マグネシウム、
粘土、けい酸塩鉱物、天然けい酸、アｌレミナ水和物、
硫酸バリウム、硫酸カルシウム、金属粉、有機充填剤（
たとえば、木粉、果実穀粉、セルローズ系等）等を、補
強材としては石綿、ガラス繊維、炭素繊維、ステンレス
繊維、アルミニウム繊維、チタン酸カリウム１ａ維、ア
ラミド繊維、ガラスピーズ、アルミニウムフレーク、等
を示し得る。Examples of fillers include carbon black, white carbon, calcium carbonate, hydrous basic magnesium carbonate,
Clay, silicate mineral, natural silicic acid, alumina hydrate,
Barium sulfate, calcium sulfate, metal powder, organic filler (
For example, asbestos, glass fiber, carbon fiber, stainless steel fiber, aluminum fiber, potassium titanate 1a fiber, aramid fiber, glass peas, aluminum flake, etc. are used as reinforcing material. can be shown.
着色剤（染料、顔料）としては、例えば酸化チタン、酸
化亜鉛、硫酸バリウム、カーボンブラック、アニリンブ
ラック、鉛白、カドミウム黄、黄鉛、ジンククロメート
、黄土、ハンザイエロー赤色酸化鉄、リソールレッド、
アリザリンレーキ、カドミウムレッド、弁柄、キナクリ
ドンレッド、コバルトバイオレット、群青、コバルトブ
ルー、フタロシアニンブルー、フタロシアニングリーン
、クロムグリーン、アルミ粉、ブロンズ粉等を示し得る
。Colorants (dyes, pigments) include, for example, titanium oxide, zinc oxide, barium sulfate, carbon black, aniline black, lead white, cadmium yellow, yellow lead, zinc chromate, loess, Hansa Yellow red iron oxide, Lysol Red,
Alizarin lake, cadmium red, Bengara, quinacridone red, cobalt violet, ultramarine, cobalt blue, phthalocyanine blue, phthalocyanine green, chrome green, aluminum powder, bronze powder, etc. may be shown.
発泡剤としては、例えば炭酸アンモニア、重炭酸ソーダ
、亜硝酸ソータ、等の無機発泡剤、ジニトロソペンタメ
チレンテトラミン、ジメチルジニトロソテレフタールア
ミド等のニトロソ系発泡剤、ベンゼンスルホニルヒドラ
ジド、ｐ−トルエンスルホニルヒドラジド、ｐ、ｐ’
オキシビス（ベンゼンスルホニルヒドラジド）、ジスル
ホンヒドラジドジフェニルスルホン等のスルホヒドラジ
ド系発泡剤、アゾビスイソブチロニトリル、アゾジカル
ボンアミド等のアゾ系発泡剤等を挙げることができる。Examples of the blowing agent include inorganic blowing agents such as ammonia carbonate, sodium bicarbonate, and nitrous acid sorter; nitroso blowing agents such as dinitrosopentamethylenetetramine and dimethyldinitrosoterephthalamide; benzenesulfonyl hydrazide; p-toluenesulfonylhydrazide; p, p'
Examples include sulfohydrazide blowing agents such as oxybis(benzenesulfonylhydrazide) and disulfonehydrazide diphenyl sulfone, and azo blowing agents such as azobisisobutyronitrile and azodicarbonamide.
架橋剤としてはラジカル重合開始剤として前出の各種過
酸化物が使用できるが、架橋助剤として例えばラウリル
メタクリレート、エチレングリコールジメタクリレート
、トリメチロールプロペントリメタクリレート等のメタ
クリレート系化合物、ジアリルフマレート、ジアリルフ
タレート、トリアリルイソシアヌレート等のアリル系化
合物、ｐ−キノンジオキシム、ジベンゾイルキノンジオ
キシム等のキノンジオキシム系化合物、またはジビニル
ベンゼン、ビニルトルエン、１．２ポリブタジエン等の
化合物を併用する事により架橋効率を高めることもでき
る。As a crosslinking agent, the various peroxides mentioned above can be used as a radical polymerization initiator, and as a crosslinking aid, for example, methacrylate compounds such as lauryl methacrylate, ethylene glycol dimethacrylate, trimethylolpropene trimethacrylate, diallyl fumarate, diallyl, etc. By using together with allyl compounds such as phthalate and triallylisocyanurate, quinone dioxime compounds such as p-quinone dioxime and dibenzoylquinone dioxime, or compounds such as divinylbenzene, vinyltoluene, and 1.2 polybutadiene. It is also possible to increase crosslinking efficiency.
本発明方法によって得られた変性重合体は、そのまま、
または該変性重合体とポリオレフィンとをブレンドした
変性重合体組成物の形で、ポリオレフィン、他の機能を
有する酸素バリヤー性樹脂、金属箔１紙等とラミネート
・シて多層フィルムの補強層あるいは接着層として使用
することができる。また、ポリオレフィンと極めて相互
溶解性がよく、またある程度他の極性ポリマーとも相互
溶解するのでポリオレフィンとポリオレフィンとはほと
んど相互溶解性のない樹脂とのポリマーアロイの相溶化
剤としての使用もできる。The modified polymer obtained by the method of the present invention can be directly used as
Or, in the form of a modified polymer composition that is a blend of the modified polymer and polyolefin, it can be laminated with polyolefin, oxygen barrier resin with other functions, metal foil, paper, etc. to form a reinforcing layer or adhesive layer of a multilayer film. It can be used as In addition, since it has extremely good mutual solubility with polyolefins and also mutually dissolves to some extent with other polar polymers, it can also be used as a compatibilizing agent for polymer alloys of polyolefins and resins in which polyolefins have almost no mutual solubility.
従って、ガラス、金属、炭素繊維と該変性重合体または
変性重合体組成物のコンポジット成形体としての利用も
可能である。Therefore, it is also possible to use glass, metal, carbon fiber and the modified polymer or modified polymer composition as a composite molded article.
［実施例］
以下に実施例、比較例を示す。実施例は本発明を例示す
るためのものであり、これをなんらμＲ定するものでな
い。[Example] Examples and comparative examples are shown below. The examples are for illustrating the present invention, and are not intended to provide any μR determination.
メルトフローレート（ＭＦＲ）はＪｉＳ Ｋ７２１０
に従って測定し、た。Melt flow rate (MFR) is JiS K7210
Measured according to the following.
式ＣＩ）にて示す化合物、不飽和カルボン酸もしくはそ
の誘導体の定量は（：”ＮＭＲ，赤外吸取スペクトル等
を使用して行なった。The compound represented by formula CI), an unsaturated carboxylic acid, or a derivative thereof was quantified using NMR, infrared absorption spectroscopy, etc.
（実施例１）
内容積０．５１２才−トクレイプに、ポリプロピレン粉
末（ＭＦＲ（２３０℃）２２ｇ／１０分）５０ｇ、アリ
ル無水コハクＩＩ！８．６ｇ、無水マレイン酸６．０ｇ
、過酸化ベンゾイル１．０ｇ及びトルエン５ｍＪ２を入
れた後１Ｍ素ガスで系内を完全に置換した６次に系内を
１００℃に昇温し撹拌しながら３時間クラフト重合反応
を行なった６反応終了後、アセトン、メチルエチルケト
ンにて十分洗浄精製した後、減圧乾燥を行なった。得ら
れた改質オレフィン重合体のＭＦＲ（２３０℃）は２．
７０ｇ／１０分で、該改質オレフィン重合体に含まれる
アリル無水コハク酸は２．３８ｗｔ％であった。また、
該改質オレフィン重合体に含まれる無水マレイン酸は２
．４６ｗｔ％であった。(Example 1) 50 g of polypropylene powder (MFR (230°C) 22 g/10 minutes), Allyl Anhydrous Amber II! 8.6g, maleic anhydride 6.0g
After adding 1.0 g of benzoyl peroxide and 5 mJ2 of toluene, the system was completely replaced with 1M elementary gas.Next, the system was heated to 100°C and a kraft polymerization reaction was carried out for 3 hours while stirring.6 Reactions After completion, the mixture was thoroughly washed and purified with acetone and methyl ethyl ketone, and then dried under reduced pressure. The MFR (230°C) of the obtained modified olefin polymer was 2.
At 70 g/10 minutes, allyl succinic anhydride contained in the modified olefin polymer was 2.38 wt%. Also,
The maleic anhydride contained in the modified olefin polymer is 2
．． It was 46wt%.
（実施例２）
実施例１において、アリル無水コハク酸８．６ｇの代わ
りに１．９デカジエニル無水コハク酸１４．５ｇを使用
した以外は実施例１にしたがった。(Example 2) Example 1 was followed except that 14.5 g of 1.9-decadienyl succinic anhydride was used instead of 8.6 g of allyl succinic anhydride.
得られた改質オレフィン重合体のＶＦＲ（２３０℃）は
３．３９ｇ７１０分で、該改質オレフィン重合体に含ま
れる１、９デカジエニル無水コハク酸は１．７８ｗｔ％
であった。また、該改質オレフィン重合体に含まれる無
水マレイン酸はｌ。The VFR (230°C) of the obtained modified olefin polymer was 3.39 g 710 minutes, and the 1,9-decadienyl succinic anhydride contained in the modified olefin polymer was 1.78 wt%.
Met. Furthermore, the amount of maleic anhydride contained in the modified olefin polymer is 1.
７８ｗｔ％であった。It was 78wt%.
（実施例３）
実施例１において、アリル無水コハクａ１８．６ｇの代
わりにメタアリル無水コハク酸９．４ｇを使用した以外
は、実施例１と同様に行なった。(Example 3) The same procedure as in Example 1 was conducted except that 9.4 g of metaallyl succinic anhydride was used instead of 18.6 g of allyl succinic anhydride a.
得られた改質オレフィン重合体のＭＦＲ（２３０℃〕は
２．８３ｇ７１０分で、該改質オレフィン重合体に含ま
れるメタアリル無水コハク酸は２．１４ｗｔ％であった
。また、該改質オレフィン重合体に含まれる無水マレイ
ン酸は２．２５ｗｔ％であった。The MFR (230°C) of the obtained modified olefin polymer was 2.83 g 710 minutes, and the metaallyl succinic anhydride contained in the modified olefin polymer was 2.14 wt%. Maleic anhydride contained in the coalescence was 2.25 wt%.
（実施例４）
アリル無水コハク＠８．６ｇの代わりに１−才ラテン−
３−無水コハク＠１２．８ｇを使用した以外は実施例１
と同様におこなった。(Example 4) Allyl anhydrous amber @ 8.6g instead of 1-year-old Latin-
3- Example 1 except that anhydrous amber @12.8g was used.
It was done in the same way.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
３．０９ｇ／１０分で、該改質オレフィン重合体に含ま
れる１−才クテン−３−無水コハク酸は１．９２ｗｔ％
であった。また、該改質オレフィン重合体に含まれる無
水マレイン酸は１．８８ｗｔ％であった。The MFR (230°C) of the obtained modified olefin polymer was 3.09 g/10 min, and the 1-year-old ctene-3-succinic anhydride contained in the modified olefin polymer was 1.92 wt%.
Met. Furthermore, the amount of maleic anhydride contained in the modified olefin polymer was 1.88 wt%.
（実施例５）
ポリプロピレン粉末５０ｇの代わりに高密度ポリエチレ
ン粉末５０ｇ （ＭＦＲ（１９０℃〉１８ｇ／１０分、
密度 ０．９５８ｇ／ｃｍ’）を使用する以外は、実施
例１と同様におこなった。(Example 5) Instead of 50 g of polypropylene powder, 50 g of high-density polyethylene powder (MFR (190°C> 18 g/10 minutes,
The same procedure as in Example 1 was carried out except that a density of 0.958 g/cm') was used.
得られた改質オレフィン重合体のＭＦＲ（１９０℃）は
１．］１ｇ／１０分で、該改質オレフィン重合体に含ま
れるアリル無水コハク酸は３５４ｗｔ％、無水マレイン
酸は３．６５ｗｔ％であった。The MFR (190°C) of the obtained modified olefin polymer was 1. ]1 g/10 minutes, the modified olefin polymer contained 354 wt% of allyl succinic anhydride and 3.65 wt% of maleic anhydride.
（実施例６）
ポリプロピレン粉末５０ｇの代わりに紛状低密度ポリエ
チレン粉末５０ｇ （ＭＦＲ（１９０℃）２０ｇ／１０
分、密度 ０．９１８ｇ／ｃｍ３）を使用する以外は、
実施例２と同様におこなった。(Example 6) Instead of 50 g of polypropylene powder, 50 g of powdered low-density polyethylene powder (MFR (190°C)) 20 g/10
, density 0.918g/cm3).
The same procedure as in Example 2 was carried out.
得られた改質オレフィン重合体のＭＦＲ（１９０℃）は
０．９２ｇ７１０分で、該改質オレフィン重合体に含ま
れる１、９デカジエニル無水コハク酸は３．０４ｗｔ％
、無水マレイン酸は３゜３０ｗｔ％であった。The MFR (190°C) of the obtained modified olefin polymer was 0.92 g 710 minutes, and the 1,9-decadienyl succinic anhydride contained in the modified olefin polymer was 3.04 wt%.
, maleic anhydride was 3°30 wt%.
（実施例７）
ポリプロピレン粉末５０ｇの化カリにエチレンプロピレ
ンランダム共重合体粉末５０ｇ（ＭＦＲ（２３０℃）１
７ｇ７１０分、エチレン含量５．２ｗｔ％）を使用する
以外は、実施例１と同様に行なった。(Example 7) 50 g of ethylene propylene random copolymer powder (MFR (230°C) 1
The same procedure as in Example 1 was carried out except that 7g, 710 minutes, ethylene content: 5.2wt%) was used.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
２．４６ｇ／１０分で、該改質オレフィン重合体に含ま
れるアリル無水コハク酸は２０４ｗｔ％、無水マレイン
酸は２．２８ｗｔ％であった。The MFR (230°C) of the obtained modified olefin polymer was 2.46 g/10 min, and the content of allyl succinic anhydride and maleic anhydride was 204 wt% and 2.28 wt%, respectively. Ta.
（実施例８）
過酸化ベンゾイル１．０ｇの代わりに、ジイソブロビル
ベーオキシジカーポネート１．０ｇを使用し、反応温度
を７０℃にする以外は実施例２と同様に行なった。(Example 8) The same procedure as in Example 2 was carried out except that 1.0 g of diisobrobyl beoxydicarbonate was used instead of 1.0 g of benzoyl peroxide and the reaction temperature was set to 70°C.
得られた改質オレフィン重合体のＶＦＲ（２３０℃）は
４．８４ｇ７１０分で、該改質オレフィン重合体に含ま
れる１、９デカジエニル無水コハク酸は１．３４ｗｔ％
、無水マレイン酸は１゜２６ｗｔ％であった。The VFR (230°C) of the obtained modified olefin polymer was 4.84 g 710 minutes, and the 1,9-decadienyl succinic anhydride contained in the modified olefin polymer was 1.34 wt%.
, maleic anhydride was 1°26 wt%.
（実施例９）
無水マレイン酸の代わりにマレイミド６０ｇを使用する
以外は、実施例１と同様に行なった。(Example 9) The same procedure as in Example 1 was carried out except that 60 g of maleimide was used instead of maleic anhydride.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
３．５４ｇ／１０分で、該改質オレフィン重合体に含ま
れるアリル無水コハク酸は２８１ｗｔ％、マレイミドは
２．３０ｗｔ％であった。The MFR (230° C.) of the obtained modified olefin polymer was 3.54 g/10 minutes, and the modified olefin polymer contained 281 wt% of allyl succinic anhydride and 2.30 wt% of maleimide.
（実施例１０）
１．９デカジェニル無水コハク酸２．８ｇ使用する以外
は、実施例２と同様に行なった。(Example 10) The same procedure as Example 2 was carried out except that 2.8 g of 1.9 decadenyl succinic anhydride was used.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
１５．９ｇ／１０分で、該改質オレフィン重合体に含ま
れる１、９デカジエニル無水コハク酸は０．８６ｗｔ％
、無水マレイン酸は０゜９４ｗｔ％であった。The MFR (230°C) of the obtained modified olefin polymer was 15.9 g/10 min, and the 1,9-decadienyl succinic anhydride contained in the modified olefin polymer was 0.86 wt%.
, maleic anhydride was 0.94 wt%.
（実施例１１） 過酸化ベンゾイルを０．２ｇ使用する以外は。(Example 11) Except for using 0.2g of benzoyl peroxide.
実施例１と同様に行なった。The same procedure as in Example 1 was carried out.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
１３．１ｇ／１０分で、該改質オレフィン重合体に含ま
れるアリル無水コハク酸は１゜０４ｗｔ％、無水マレイ
ン酸はｌ 、２２ｗｔ％であった。The MFR (230°C) of the obtained modified olefin polymer was 13.1 g/10 min, and the modified olefin polymer contained 1°04 wt% of allyl succinic anhydride and 22 wt% of maleic anhydride. Met.
（比較例１）
無水マレイン酸を使用しない以外は実施例１と同様にお
こなった。(Comparative Example 1) The same procedure as in Example 1 was carried out except that maleic anhydride was not used.
得られた改質オレフィン重合体のＭＦＲ（２３０℃）は
４ｓ、２ｇ／１０分で、該改質オレフィン重合体に含ま
れるアリル無水コハク酸はＯ２０８ｗｔ％であった。The MFR (230° C.) of the obtained modified olefin polymer was 4 s, 2 g/10 min, and the allyl succinic anhydride contained in the modified olefin polymer was O208 wt%.
（比較例２ン
アリル無水コハク＠８．６ｇの代わりに１，９デカジェ
ニル無水コハク＠１４．５ｇを使用する以外は、比較例
１と同様におこなった、得られた改質オレフィン重合体
のＭＦＲ（２３０℃）は４８．７ｇ／１０分で、該改質
オレフィン重合体に含まれる１、９デカジエニル無水コ
ハク酸は０．０３ｗｔ％であった。(Comparative Example 2 MFR of the obtained modified olefin polymer ( (230°C) was 48.7 g/10 minutes, and the amount of 1,9-decadienyl succinic anhydride contained in the modified olefin polymer was 0.03 wt%.
以上の実施例１〜１１及び比較例１〜２の結果をまとめ
、第１表に一覧表としてしめす。The results of the above Examples 1 to 11 and Comparative Examples 1 to 2 are summarized and shown in Table 1.
ｃ以下余白）
（参考例）
実施例１．２．３．４．５．６．９．及び比較例１．２
で得られた変性重合体を、ポリプロピレン（ＭＦＲ（２
３０℃）５．５ｇ／１０分）とブレンドして、該変性重
合体機が１０重量％である変性重合体組成物を得た。Margin below c) (Reference example) Example 1.2.3.4.5.6.9. and Comparative Example 1.2
The modified polymer obtained in
(30° C.) 5.5 g/10 min) to obtain a modified polymer composition having 10% by weight of the modified polymer.
該変性重合体組成物及びエチレン−ビニルアルコール共
重合体（エチレン含有量：３２モル％）を４０ｍｍ、４
５ｍｍの二種二層共押出し成形機を用いて、ダイス温度
２２０℃、通水状態のチルロールを使用して二種二層フ
ィルム（厚み３０ｕｍ ｘ ２ ）を作った。このよう
にして得られたラミネートフィルムの１８０°剥離試験
を剥離速度２００ｍｍ／分）にて評価した。その結果を
第２表にしめす。The modified polymer composition and ethylene-vinyl alcohol copolymer (ethylene content: 32 mol%) were mixed into 40 mm, 4
Using a 5 mm two-type, two-layer coextrusion molding machine, a two-type, two-layer film (thickness: 30 um x 2) was produced using a chill roll with a die temperature of 220° C. and a water-permeable state. A 180° peel test of the thus obtained laminate film was evaluated at a peel rate of 200 mm/min. The results are shown in Table 2.
（以下余白）
以上の結果より、本発明方法により改質された変性重合
体はポリオレフィンとの相溶性に優れており、更にポリ
オレフィンとブレンドした重合体組成物であって６工チ
レンービニルアルコール系共重合体と高い接着力を示す
ことが判る。(Left below) From the above results, the modified polymer modified by the method of the present invention has excellent compatibility with polyolefin, and is a polymer composition blended with polyolefin. It can be seen that it exhibits high adhesive strength with the copolymer.
［発明の効果］
本発明のポリオレフィンのグラフト重合の方法により不
飽和脂肪族カルボン酸及びその誘導体を多量にグラフト
重合させることが可能になった。[Effects of the Invention] The polyolefin graft polymerization method of the present invention has made it possible to graft-polymerize large amounts of unsaturated aliphatic carboxylic acids and derivatives thereof.
このようにして得られる不飽和脂肪族カルボン酸及びそ
の誘導体をグラフト重合した変性重合体は、そのまま、
または該変性重合体とポリオレフィンとをブレンドした
変性重合体組成物の形で、ポリオレフィン、他の機能を
有する酸素バリヤー性樹脂、金属箔、紙等とラミネート
して多層フィルムの補強層あるいは接着層として使用す
ることができる。また、ポリオレフィンと極めて相互溶
解性がよく、またある程度他の極性ポリマーとも相互溶
解するのでポリオレフィンとポリオレフィンとはほとん
ど相互溶解性のない樹脂とのポリマーアロイの相溶化剤
としての使用もできる。The modified polymer obtained by graft polymerization of the unsaturated aliphatic carboxylic acid and its derivatives obtained in this way can be used as it is.
Or, in the form of a modified polymer composition that is a blend of the modified polymer and polyolefin, it can be laminated with polyolefin, oxygen barrier resin with other functions, metal foil, paper, etc., and used as a reinforcing layer or adhesive layer of a multilayer film. can be used. In addition, since it has extremely good mutual solubility with polyolefins and also mutually dissolves to some extent with other polar polymers, it can also be used as a compatibilizing agent for polymer alloys of polyolefins and resins in which polyolefins have almost no mutual solubility.
従って、ガラス、金属、炭素繊維と該変性重合体または
変性重合体組成物のコンポジット成形体としての利用ら
可能である。Therefore, it is possible to use glass, metal, carbon fiber and the modified polymer or modified polymer composition as a composite molded article.
Claims (4)
（ I ）にて示される化合物 ▲数式、化学式、表等があります▼（ I ） 〔Ｒ＿１＝Ｈ，ＣＨ＿３Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿
５およびＲ＿６＝Ｈ、コハク酸、コハク酸無水物または
コハク酸ジアルキルエステルｒ＝０〜２０、ｓ＝０また
は１、ｔ＝０または１を表わす。〕 をグラフト重合するにあたり、不飽和カルボン酸および
／またはその誘導体を共存させることを特徴とする変性
重合体の製造方法。(1) A compound represented by the following formula (I) using a radical initiator in polyolefin ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [R_1=H, CH_3R_2, R_3, R_4, R_
5 and R_6=H, succinic acid, succinic anhydride or succinic dialkyl ester r=0 to 20, s=0 or 1, t=0 or 1. ] A method for producing a modified polymer, which comprises coexisting an unsaturated carboxylic acid and/or a derivative thereof during graft polymerization.
イン酸、マレイン酸、マレイン酸ジアルキルエステル、
Ｎ−アルキルフェニル置換マレイミドおよびマレイミド
から選ばれた少なくとも１種の化合物である特許請求の
範囲第１項記載の方法。(2) Unsaturated carboxylic acid or its derivative is maleic anhydride, maleic acid, maleic acid dialkyl ester,
The method according to claim 1, which is at least one compound selected from N-alkylphenyl-substituted maleimides and maleimides.
飽和カルボン酸および／またはその誘導体のモル比が０
．７〜１．５を共存させる特許請求の範囲第１項記載の
方法。(3) The molar ratio of the unsaturated carboxylic acid and/or its derivative to 1 mole of the compound represented by formula (I) is 0
．． 7 to 1.5 coexist in the method according to claim 1.
および不飽和カルボン酸および／またはその誘導体を共
存させてグラフト重合する場合、無溶媒または溶媒を使
用してもポリオレフィンが溶解または溶融しない状態で
グラフト重合させる特許請求の範囲第１項記載の方法。(4) When graft polymerizing a polyolefin, a compound represented by formula (I), and an unsaturated carboxylic acid and/or its derivative in the coexistence, the polyolefin is not dissolved or melted even if no solvent is used or a solvent is used. The method according to claim 1, wherein graft polymerization is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3580790A JPH03239710A (en) | 1990-02-15 | 1990-02-15 | Production of modified polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3580790A JPH03239710A (en) | 1990-02-15 | 1990-02-15 | Production of modified polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03239710A true JPH03239710A (en) | 1991-10-25 |
Family
ID=12452202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3580790A Pending JPH03239710A (en) | 1990-02-15 | 1990-02-15 | Production of modified polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03239710A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010539258A (en) * | 2007-09-11 | 2010-12-16 | ダウ グローバル テクノロジーズ インコーポレイティド | Method for producing carboxylated ethylene polymer blend |
-
1990
- 1990-02-15 JP JP3580790A patent/JPH03239710A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010539258A (en) * | 2007-09-11 | 2010-12-16 | ダウ グローバル テクノロジーズ インコーポレイティド | Method for producing carboxylated ethylene polymer blend |
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