JP2023140475A - graft copolymer - Google Patents
graft copolymer Download PDFInfo
- Publication number
- JP2023140475A JP2023140475A JP2022046330A JP2022046330A JP2023140475A JP 2023140475 A JP2023140475 A JP 2023140475A JP 2022046330 A JP2022046330 A JP 2022046330A JP 2022046330 A JP2022046330 A JP 2022046330A JP 2023140475 A JP2023140475 A JP 2023140475A
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- JP
- Japan
- Prior art keywords
- mass
- polymer
- acrylonitrile
- parts
- graft copolymer
- 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
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- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 52
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229920000642 polymer Polymers 0.000 claims abstract description 86
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 39
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims description 64
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920002972 Acrylic fiber Polymers 0.000 abstract description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 84
- 238000006243 chemical reaction Methods 0.000 description 81
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 48
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 43
- 235000010323 ascorbic acid Nutrition 0.000 description 42
- 229960005070 ascorbic acid Drugs 0.000 description 42
- 239000011668 ascorbic acid Substances 0.000 description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 26
- -1 vinyl halides Chemical class 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 21
- 238000010526 radical polymerization reaction Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 13
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 12
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- XIMFCGSNSKXPBO-UHFFFAOYSA-N ethyl 2-bromobutanoate Chemical compound CCOC(=O)C(Br)CC XIMFCGSNSKXPBO-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 6
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VLSVVMPLPMNWBH-UHFFFAOYSA-N Dihydro-5-propyl-2(3H)-furanone Chemical compound CCCC1CCC(=O)O1 VLSVVMPLPMNWBH-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- 239000001730 (5R)-5-butyloxolan-2-one Substances 0.000 description 1
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 1
- LOWMYOWHQMKBTM-UHFFFAOYSA-N 1-butylsulfinylbutane Chemical compound CCCCS(=O)CCCC LOWMYOWHQMKBTM-UHFFFAOYSA-N 0.000 description 1
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- MJWNJEJCQHNDNM-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)sulfinylbenzene Chemical compound C1=CC(C)=CC=C1S(=O)C1=CC=C(C)C=C1 MJWNJEJCQHNDNM-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- WUIJTQZXUURFQU-UHFFFAOYSA-N 1-methylsulfonylethene Chemical compound CS(=O)(=O)C=C WUIJTQZXUURFQU-UHFFFAOYSA-N 0.000 description 1
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- MCDJZKPTBCWNSJ-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylsulfinyl)propane Chemical compound CC(C)CS(=O)CC(C)C MCDJZKPTBCWNSJ-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- WFJXYIUAMJAURQ-UHFFFAOYSA-N 2-propan-2-ylsulfinylpropane Chemical compound CC(C)S(=O)C(C)C WFJXYIUAMJAURQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FGSUUFDRDVJCLT-UHFFFAOYSA-N 3-methylazepan-2-one Chemical compound CC1CCCCNC1=O FGSUUFDRDVJCLT-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101500000959 Bacillus anthracis Protective antigen PA-20 Proteins 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 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 1
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- 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
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- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- 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
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、アクリル系樹脂を幹ポリマーとするグラフト共重合体に関する。 The present invention relates to a graft copolymer having an acrylic resin as a backbone polymer.
アクリロニトリルとハロゲン化ビニル等とを共重合したアクリル系樹脂で構成されるアクリル系繊維は、人工毛髪、難燃性素材、及びパイル布帛等のさまざまな製品に用いられてきた。従来から、アクリル系樹脂は、軟化温度よりも分解開始温度が低く、溶融加工すると分解してしまうため、湿式紡糸法で繊維化されてきた。しかし、湿式紡糸法の場合、排水負荷が高く、溶剤の回収コストが高い。 Acrylic fibers made of acrylic resins made by copolymerizing acrylonitrile and vinyl halides have been used in various products such as artificial hair, flame-retardant materials, and pile fabrics. Conventionally, acrylic resins have been made into fibers by wet spinning because their decomposition initiation temperature is lower than their softening temperature and they decompose when melt processed. However, in the case of wet spinning, the wastewater load is high and the cost of recovering the solvent is high.
そこで、特許文献１では、アクリロニトリルと、その他のエチレン性不飽和モノマーとを共重合したアクリル樹脂を、エチレン性不飽和モノマーからなるマクロモノマーでグラフトしたグラフト共重合体を用いることにより、溶融紡糸法によりアクリル系繊維を作製できることが開示されている。 Therefore, in Patent Document 1, by using a graft copolymer obtained by grafting an acrylic resin obtained by copolymerizing acrylonitrile and other ethylenically unsaturated monomers with a macromonomer consisting of an ethylenically unsaturated monomer, a melt spinning method is proposed. It is disclosed that acrylic fibers can be produced by.
アクリル系繊維が溶融紡糸法で作成できるようになったことから、溶融紡糸法には、湿式紡糸法等の従来の加工方法との機能的な差別化が求められており、また、アクリル系樹脂には、さまざまな溶融加工法への適応が求められている。例えば、機能の差別化を図ったり、加工適用可能性を広げたりするために、強度及び流動性の一方又は両方に優れたアクリル系樹脂が求められている。 Since acrylic fibers can now be created by melt-spinning, there is a need for melt-spinning to be functionally differentiated from conventional processing methods such as wet spinning. There is a need for adaptation to various melt processing methods. For example, acrylic resins with excellent strength and fluidity, or both, are required in order to differentiate functionality and expand processing applicability.
本発明は、上記課題に鑑みてなされたものであり、強度及び流動性の一方又は両方に優れたアクリル系繊維を作製するのに適したグラフト共重合体を提供することを目的とする。 The present invention was made in view of the above problems, and an object of the present invention is to provide a graft copolymer suitable for producing an acrylic fiber having excellent strength and fluidity, or both.
本発明者は、上記課題を解決するために鋭意研究を重ねた結果、グラフト共重合体において、枝ポリマーの構成原料となるマクロモノマー中にランダムに、アクリロニトリルに由来する構成単位を所定量導入することにより、強度及び流動性の一方又は両方の向上といった従来のグラフト共重合体には見られなかった特性を付与できることを見出し、本発明を完成した。 As a result of intensive research to solve the above problems, the present inventor randomly introduced a predetermined amount of acrylonitrile-derived structural units into the macromonomer that is the constituent raw material of the branch polymer in the graft copolymer. The present invention was completed based on the discovery that properties not seen in conventional graft copolymers, such as improvement in either or both of strength and fluidity, can be imparted by this method.
本発明の一態様は、アクリロニトリル（ａ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ａ２）に由来する構成単位を含むアクリル系樹脂からなる幹ポリマー（Ａ）と、
アクリロニトリル（ｂ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位を含む重合体からなる枝ポリマー（Ｂ）と、を含み、
上記枝ポリマー（Ｂ）は、第１の末端と第２の末端とを有し、上記第２の末端で上記幹ポリマー（Ａ）にグラフトしている、グラフト共重合体であって、
前記枝ポリマー（Ｂ）は、前記第１の末端を含み、かつ、前記枝ポリマー（Ｂ）中の全構成単位の数の半数の構成単位を含む末端領域中に、前記アクリロニトリル（ｂ１）に由来する全構成単位の３０モル％超７０モル％未満を含み、
上記アクリロニトリル（ｂ１）に由来する構成単位の含有量が、上記枝ポリマー（Ｂ）中の全構成単位に対し、３モル％以上５０モル％以下である、グラフト共重合体である。
One aspect of the present invention is a backbone polymer (A) made of an acrylic resin containing a structural unit derived from acrylonitrile (a1) and a structural unit derived from another ethylenically unsaturated monomer (a2);
A branched polymer (B) consisting of a polymer containing a structural unit derived from acrylonitrile (b1) and a structural unit derived from another ethylenically unsaturated monomer (b2),
The branch polymer (B) is a graft copolymer having a first end and a second end, and is grafted to the trunk polymer (A) at the second end,
The branched polymer (B) contains a compound derived from the acrylonitrile (b1) in the terminal region that includes the first end and contains half the number of structural units of the total number of structural units in the branched polymer (B). Containing more than 30 mol% and less than 70 mol% of all structural units,
It is a graft copolymer in which the content of structural units derived from the acrylonitrile (b1) is 3 mol% or more and 50 mol% or less based on all the structural units in the branched polymer (B).
本発明によれば、強度及び流動性の一方又は両方に優れたグラフト共重合体を提供することができる。本発明に係るグラフト共重合体を用いて、強度及び流動性の一方又は両方に優れたアクリル系繊維を好適に作製することができる。 According to the present invention, it is possible to provide a graft copolymer that is excellent in either or both of strength and fluidity. Using the graft copolymer according to the present invention, acrylic fibers having excellent strength and/or fluidity can be suitably produced.
本発明のグラフト共重合体をランダム型グラフト共重合体という場合がある。以下、このグラフト共重合体について、説明する。 The graft copolymer of the present invention may be referred to as a random graft copolymer. This graft copolymer will be explained below.
＜ランダム型グラフト共重合体＞
ランダム型グラフト共重合体は、アクリロニトリル（ａ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ａ２）に由来する構成単位を含むアクリル系樹脂からなる幹ポリマー（Ａ）と、
アクリロニトリル（ｂ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位を含む重合体からなる枝ポリマー（Ｂ）と、を含む。
<Random type graft copolymer>
The random graft copolymer comprises a backbone polymer (A) made of an acrylic resin containing a structural unit derived from acrylonitrile (a1) and a structural unit derived from another ethylenically unsaturated monomer (a2);
A branched polymer (B) consisting of a polymer containing a structural unit derived from acrylonitrile (b1) and a structural unit derived from another ethylenically unsaturated monomer (b2).
（枝ポリマー（Ｂ））
枝ポリマー（Ｂ）は、第１の末端と第２の末端とを有し、上記第２の末端で上記幹ポリマー（Ａ）にグラフトしている。上記第１の末端は、枝ポリマー（Ｂ）の中で、上記幹ポリマー（Ａ）から最も遠い位置に存在する自由端である。
枝ポリマー（Ｂ）は、上記第１の末端を含む末端領域と、該末端領域以外の領域（以下、「非末端領域」ともいう。）とからなる。
枝ポリマー（Ｂ）は、前記第１の末端を含み、かつ、前記枝ポリマー（Ｂ）中の全構成単位の数の半数の構成単位を含む末端領域中に、前記アクリロニトリル（ｂ１）に由来する全構成単位の３０モル％超７０モル％未満を含む。一方で、枝ポリマー（Ｂ）は、非末端領域中にも、前記アクリロニトリル（ｂ１）に由来する全構成単位の３０モル％超７０モル％未満を含む。よって、上記末端領域と上記非末端領域との間で、前記アクリロニトリル（ｂ１）に由来する構成単位の分布に大きな偏りが生じにくく、前記アクリロニトリル（ｂ１）に由来する構成単位は、枝ポリマー（Ｂ）の全体にわたって一定範囲内の密度で存在しやすい。本明細書では、このような構造を、「ランダム型構造」と称する。
(Branch polymer (B))
The branch polymer (B) has a first end and a second end, and is grafted to the trunk polymer (A) at the second end. The first end is the free end of the branch polymer (B) that is located farthest from the trunk polymer (A).
The branch polymer (B) consists of a terminal region including the first terminal and a region other than the terminal region (hereinafter also referred to as "non-terminal region").
The branch polymer (B) contains the first end and contains half the number of structural units of the total number of structural units in the branch polymer (B), which is derived from the acrylonitrile (b1). Contains more than 30 mol% and less than 70 mol% of all structural units. On the other hand, the branch polymer (B) contains more than 30 mol% and less than 70 mol% of the total structural units derived from the acrylonitrile (b1) also in the non-terminal region. Therefore, between the terminal region and the non-terminal region, a large deviation in the distribution of the structural units derived from the acrylonitrile (b1) is unlikely to occur, and the structural units derived from the acrylonitrile (b1) are ) tend to exist at a density within a certain range throughout the area. In this specification, such a structure is referred to as a "random type structure."
枝ポリマー（Ｂ）は、高強度及び高流動性の一方又は両方の観点から、上記末端領域中に、アクリロニトリル（ｂ１）に由来する全構成単位の３０モル％超７０モル％未満、好ましくは３５モル％以上６５モル％以下、より好ましくは４０モル％以上６０モル％以下、更により好ましくは４５モル％以上５５モル％以下を含む。 From the viewpoint of one or both of high strength and high fluidity, the branch polymer (B) contains more than 30 mol% but less than 70 mol%, preferably 35 mol% of the total structural units derived from acrylonitrile (b1), from the viewpoint of one or both of high strength and high fluidity. It contains mol% or more and 65 mol% or less, more preferably 40 mol% or more and 60 mol% or less, and even more preferably 45 mol% or more and 55 mol% or less.
上記末端領域中のアクリロニトリル（ｂ１）に由来する構成単位の割合は、高強度及び高流動性の一方又は両方の観点から、末端領域中の全構成単位の数に対し、好ましくは１０％以上１００％以下であり、より好ましくは１５％以上１００％以下である。上記末端領域中のアクリロニトリル（ｂ１）に由来する構成単位の割合が１００％未満の場合、上記末端領域中には、上記その他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位が含まれる。
上記末端領域中のアクリロニトリル（ｂ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位の比（ｂ１／ｂ２）は、好ましくは１０／９０以上１００／０以下であり、より好ましくは１５／８５以上１００／０以下である。
The proportion of structural units derived from acrylonitrile (b1) in the terminal region is preferably 10% or more with respect to the total number of structural units in the terminal region, from the viewpoint of high strength and/or high fluidity. % or less, more preferably 15% or more and 100% or less. When the proportion of structural units derived from acrylonitrile (b1) in the terminal region is less than 100%, the terminal region contains structural units derived from the other ethylenically unsaturated monomer (b2).
The ratio (b1/b2) of the structural unit derived from acrylonitrile (b1) and the structural unit derived from the other ethylenically unsaturated monomer (b2) in the terminal region is preferably 10/90 or more and 100/0 or less. Yes, and more preferably 15/85 or more and 100/0 or less.
ランダム型構造を有する枝ポリマー（Ｂ）の構成原料であるその他のエチレン性不飽和モノマー（ｂ２）としては、（メタ）アクリル酸エステル系モノマー、スチレン系モノマー、ニトリル基含有ビニルモノマー、及びアミド基含有ビニルモノマーからなる群より選ばれる１種以上が好ましい。なお、本明細書において、（メタ）アクリル酸とは、アクリル酸及び／又はメタクリル酸を意味する。 Other ethylenically unsaturated monomers (b2) that are constituent raw materials of the branched polymer (B) having a random structure include (meth)acrylic acid ester monomers, styrene monomers, nitrile group-containing vinyl monomers, and amide groups. One or more types selected from the group consisting of vinyl monomers are preferred. In addition, in this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid.
（メタ）アクリル酸エステル系モノマーとしては、例えば、炭素原子数が１以上１８以下の脂肪族炭化水素基を有する(メタ)アクリル酸脂肪族炭化水素エステル、(メタ)アクリル酸脂環式炭化水素エステル、（メタ）アクリル酸芳香族炭化水素エステル、（メタ）アクリル酸アラルキルエステルが挙げられる。 Examples of (meth)acrylic acid ester monomers include (meth)acrylic acid aliphatic hydrocarbon esters having an aliphatic hydrocarbon group having 1 to 18 carbon atoms, and (meth)acrylic acid alicyclic hydrocarbons. Examples include ester, (meth)acrylic acid aromatic hydrocarbon ester, and (meth)acrylic acid aralkyl ester.
炭素原子数が１以上１８以下の脂肪族炭化水素基を有する(メタ)アクリル酸脂肪族炭化水素エステルとしては、例えば、（メタ）アクリル酸、（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ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸ｎ－ヘプチル、（メタ）アクリル酸ｎ－オクチル、（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）アクリル酸ドデシル、（メタ）アクリル酸ステアリルが挙げられる。
(メタ)アクリル酸脂環式炭化水素エステルとしては、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニルが挙げられる。
(メタ)アクリル酸芳香族炭化水素エステルとしては、例えば、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイルが挙げられる。
（メタ）アクリル酸アラルキルエステルとしては、例えば、（メタ）アクリル酸ベンジルが挙げられる。
Examples of (meth)acrylic acid aliphatic hydrocarbon esters having an aliphatic hydrocarbon group having 1 to 18 carbon atoms include (meth)acrylic acid, methyl (meth)acrylate, and ethyl (meth)acrylate. , n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate , n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate , dodecyl (meth)acrylate, and stearyl (meth)acrylate.
Examples of the (meth)acrylic acid alicyclic hydrocarbon ester include cyclohexyl (meth)acrylate and isobornyl (meth)acrylate.
Examples of the (meth)acrylic acid aromatic hydrocarbon ester include phenyl (meth)acrylate and tolyl (meth)acrylate.
Examples of (meth)acrylic acid aralkyl esters include benzyl (meth)acrylate.
また、前述した（メタ）アクリル酸エステル系モノマーとしては、例えば、エステル部分にヘテロ原子を有する（メタ）アクリル酸エステル系モノマーを用いてもよい。ヘテロ原子としては、特に限定されず、例えば、酸素（Ｏ）、フッ素（Ｆ）、窒素（Ｎ）等が挙げられる。上記エステル部分にヘテロ原子を有する（メタ）アクリル酸エステル系モノマーとしては、例えば、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸３－メトキシブチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２－アミノエチル、γ－（メタクリロイルオキシプロピル）トリメトキシシラン、（メタ）アクリル酸のエチレンオキサイド付加物、（メタ）アクリル酸トリフルオロメチルメチル、（メタ）アクリル酸２－トリフルオロメチルエチル、（メタ）アクリル酸２－パーフルオロエチルエチル、（メタ）アクリル酸２－パーフルオロエチル－２－パーフルオロブチルエチル、（メタ）アクリル酸２－パーフルオロエチル、（メタ）アクリル酸パーフルオロメチル、（メタ）アクリル酸ジパーフルオロメチルメチル、（メタ）アクリル酸２－パーフルオロメチル－２－パーフルオロエチルメチル、（メタ）アクリル酸２－パーフルオロヘキシルエチル、（メタ）アクリル酸２－パーフルオロデシルエチル、及び（メタ）アクリル酸２－パーフルオロヘキサデシルエチル等が挙げられる。 Further, as the above-mentioned (meth)acrylic acid ester monomer, for example, a (meth)acrylic acid ester monomer having a hetero atom in the ester moiety may be used. Heteroatoms are not particularly limited, and include, for example, oxygen (O), fluorine (F), nitrogen (N), and the like. Examples of the (meth)acrylic acid ester monomer having a hetero atom in the ester moiety include 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, ethylene oxide adduct of (meth)acrylic acid, Trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth)acrylate Ethyl, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate , 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.
スチレン系モノマーとしては、例えば、スチレン、ビニルトルエン、α－メチルスチレン、クロルスチレン、スチレンスルホン酸及びその塩が挙げられる。 Examples of styrenic monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, and salts thereof.
ニトリル基含有ビニル系モノマーとしては、アクリロニトリル以外のモノマーであって、例えば、メタクリロニトリルが挙げられる。 Examples of the nitrile group-containing vinyl monomer include monomers other than acrylonitrile, such as methacrylonitrile.
アミド基含有ビニル系モノマーとしては、例えば、アクリルアミド、及びメタクリルアミドが挙げられる。 Examples of the amide group-containing vinyl monomer include acrylamide and methacrylamide.
枝ポリマー（Ｂ）の構成単位の数は、高強度及び高流動性の一方又は両方の観点から、好ましくは１０個以上４００個以下であり、より好ましくは１５個以上１５０個以下である。 The number of structural units of the branched polymer (B) is preferably 10 to 400, more preferably 15 to 150, from the viewpoint of one or both of high strength and high fluidity.
枝ポリマー（Ｂ）中のアクリロニトリル（ｂ１）に由来する構成単位の含有量は、枝ポリマー（Ｂ）中の全構成単位に対し、高強度及び高流動性の一方又は両方の観点から、３モル％以上５０モル％以下であり、好ましくは４モル％以上４５モル％以下であり、より好ましくは４．５モル％以上４２．５モル％以下である。
枝ポリマー（Ｂ）中のアクリロニトリル（ｂ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位のモル含有量の比（ｂ１／ｂ２）は、好ましくは０．１／９９．９以上２０／８０以下であり、より好ましくは１／９９以上１５／８５以下である。
The content of the structural unit derived from acrylonitrile (b1) in the branched polymer (B) is 3 mol based on all the structural units in the branched polymer (B) from the viewpoint of high strength and/or high fluidity. % or more and 50 mol% or less, preferably 4 mol% or more and 45 mol% or less, and more preferably 4.5 mol% or more and 42.5 mol% or less.
The molar content ratio (b1/b2) of the structural unit derived from acrylonitrile (b1) and the structural unit derived from the other ethylenically unsaturated monomer (b2) in the branched polymer (B) is preferably 0.1. /99.9 or more and 20/80 or less, more preferably 1/99 or more and 15/85 or less.
枝ポリマー（Ｂ）の数平均分子量（Ｍｎ）は、高強度及び高流動性の一方又は両方の観点から、好ましくは１０００以上５００００以下であり、より好ましくは２０００以上２００００以下である。枝ポリマー（Ｂ）は、分子量分布が狭い観点から、質量平均分子量Ｍｗと数平均分子量Ｍｎの比（Ｍｗ／Ｍｎ）が１．１以上１．５以下であることが好ましい。 The number average molecular weight (Mn) of the branched polymer (B) is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 20,000 or less, from the viewpoint of one or both of high strength and high fluidity. From the viewpoint of narrow molecular weight distribution, the branch polymer (B) preferably has a ratio (Mw/Mn) of mass average molecular weight Mw to number average molecular weight Mn of 1.1 or more and 1.5 or less.
（幹ポリマー（Ａ））
幹ポリマー（Ａ）は、前述したように、アクリロニトリル（ａ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ａ２）に由来する構成単位を含むアクリル系樹脂からなる。
(Stem polymer (A))
As described above, the backbone polymer (A) is made of an acrylic resin containing a structural unit derived from acrylonitrile (a1) and a structural unit derived from another ethylenically unsaturated monomer (a2).
幹ポリマー（Ａ）の構成原料であるその他のエチレン性不飽和モノマー（ａ２）としては、酢酸ビニルが好ましい。 Vinyl acetate is preferable as the other ethylenically unsaturated monomer (a2) which is a constituent raw material of the backbone polymer (A).
上記アクリロニトリル（ａ１）に由来する構成単位の含有量は、高強度の観点から、ランダム型グラフト共重合体の全体に対し、好ましくは１５質量％以上８５質量％以下であり、より好ましくは３０質量％以上７０質量％以下である。上記その他のエチレン性不飽和モノマー（ａ２）に由来する構成単位の含有量は、高強度及び高流動性の一方又は両方の観点から、ランダム型グラフト共重合体の全体に対し、好ましくは１５質量％以上８５質量％以下であり、より好ましくは３０質量％以上７０質量％以下である。上記枝ポリマー（Ｂ）の含有量は、高強度及び高流動性の一方又は両方の観点から、ランダム型グラフト共重合体の全体に対し、好ましくは０．５質量％以上４０質量％以下であり、より好ましくは１質量％以上３０質量％以下である。 From the viewpoint of high strength, the content of the structural unit derived from acrylonitrile (a1) is preferably 15% by mass or more and 85% by mass or less, more preferably 30% by mass, based on the entire random graft copolymer. % or more and 70% by mass or less. The content of the structural unit derived from the other ethylenically unsaturated monomer (a2) is preferably 15% by mass based on the entire random graft copolymer from the viewpoint of high strength and/or high fluidity. % or more and 85% by mass or less, more preferably 30% by mass or more and 70% by mass or less. The content of the branch polymer (B) is preferably 0.5% by mass or more and 40% by mass or less based on the entire random graft copolymer from the viewpoint of high strength and high fluidity or both. , more preferably 1% by mass or more and 30% by mass or less.
ランダム型グラフト共重合体の質量平均分子量（Ｍｗ）は、高強度及び高流動性の一方又は両方の観点から、好ましくは１００００以上３０００００以下であり、より好ましくは２００００以上１５００００以下である。 The mass average molecular weight (Mw) of the random graft copolymer is preferably 10,000 or more and 300,000 or less, more preferably 20,000 or more and 150,000 or less, from the viewpoint of one or both of high strength and high fluidity.
＜グラフト共重合体の製造方法＞
ランダム型グラフト共重合体は、例えば、幹ポリマー（Ａ）を構成するアクリル系樹脂を調製するための上記アクリロニトリル（ａ１）及び上記その他のエチレン性不飽和モノマー（ａ２）、並びに、上記枝ポリマー（Ｂ）を構成するマクロモノマーを共重合させることによって製造することができる。
<Method for producing graft copolymer>
The random graft copolymer is, for example, the above acrylonitrile (a1) and the above other ethylenically unsaturated monomer (a2) for preparing the acrylic resin constituting the trunk polymer (A), and the above branch polymer ( It can be produced by copolymerizing macromonomers constituting B).
マクロモノマーとは、重合体の末端に反応性官能基を有するオリゴマー分子を意味する。上記枝ポリマー（Ｂ）を構成するマクロモノマーは、上記アクリロニトリル（ｂ１）に由来する構成単位及び上記その他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位を含む共重合体の末端に、反応性官能基として、例えば、アリル基、ビニルシリル基、ビニルエーテル基、ジシクロペンタジエニル基、及び下記一般式（１）で表される重合性の炭素－炭素二重結合を有する基からなる群から選ばれる重合性の炭素－炭素二重結合を有する基を、少なくとも１分子あたり１個有することが好ましい。該マクロモノマーは通常ラジカル重合によって製造することができる。特に、上記アクリロニトリル（ａ１）や上記その他のエチレン性不飽和モノマー（ａ２）との反応性が良好なことから、上記マクロモノマーにおいて、反応性官能基は下記一般式（１）で表される重合性の炭素－炭素二重結合を有することが好ましい。 Macromonomer means an oligomer molecule having a reactive functional group at the end of the polymer. The macromonomer constituting the branched polymer (B) reacts at the end of a copolymer containing a structural unit derived from the acrylonitrile (b1) and a structural unit derived from the other ethylenically unsaturated monomer (b2). As a functional group, for example, from the group consisting of an allyl group, a vinylsilyl group, a vinyl ether group, a dicyclopentadienyl group, and a group having a polymerizable carbon-carbon double bond represented by the following general formula (1). It is preferable that each molecule contains at least one selected group having a polymerizable carbon-carbon double bond. The macromonomer can usually be produced by radical polymerization. In particular, since the reactivity with the above acrylonitrile (a1) and the above other ethylenically unsaturated monomers (a2) is good, the reactive functional group in the above macromonomer is capable of polymerization represented by the following general formula (1). It is preferable to have a carbon-carbon double bond.
ＣＨ２＝Ｃ（Ｒ）－Ｃ（Ｏ）Ｏ－ （１）
一般式（１）中、Ｒは、水素原子又は炭素原子数１以上２０以下の有機基を表す。Ｒの具体例としては、例えば、好ましくは－Ｈ、－ＣＨ３、－ＣＨ２ＣＨ３、－（ＣＨ２）ｎＣＨ３（ｎは２以上１９以下の整数を表す）、－Ｃ６Ｈ５、－ＣＨ２ＯＨ、及び－ＣＮからなる群から選ばれる基であり、より好ましくは－Ｈ、及び－ＣＨ３からなる群から選ばれる基である。
CH 2 =C(R)-C(O)O- (1)
In general formula (1), R represents a hydrogen atom or an organic group having 1 or more and 20 or less carbon atoms. Specific examples of R include, for example, preferably -H, -CH 3 , -CH 2 CH 3 , -(CH 2 ) n CH 3 (n represents an integer of 2 to 19), -C 6 H 5 , -CH 2 OH, and -CN, more preferably -H, and -CH 3 .
上記マクロモノマーの主鎖である、上記アクリロニトリル（ｂ１）に由来する構成単位及び上記その他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位を含む共重合体は、ラジカル重合によって製造される。ラジカル重合法は、重合開始剤としてアゾ系化合物、過酸化物等を使用して、特定の官能基を有するモノマーとビニル系モノマーとを単に共重合させる「一般的なラジカル重合法」と、末端等の制御された位置に特定の官能基を導入することが可能な「制御ラジカル重合法」に分類できる。 A copolymer containing a structural unit derived from the acrylonitrile (b1) and a structural unit derived from the other ethylenically unsaturated monomer (b2), which is the main chain of the macromonomer, is produced by radical polymerization. Radical polymerization methods are divided into "general radical polymerization methods" in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, peroxide, etc. as a polymerization initiator, and It can be classified as a ``controlled radical polymerization method'' that allows the introduction of specific functional groups into controlled positions.
「一般的なラジカル重合法」は、特定の官能基を有するモノマーは確率的にしか重合体中に導入されないので、官能化率の高い重合体を得ようとした場合には、このモノマーをかなり大量に使用する必要がある。またフリーラジカル重合であるため、分子量分布が広く、粘度の低い重合体は得にくい。 In the "general radical polymerization method," monomers with specific functional groups are only introduced stochastically into the polymer, so when trying to obtain a polymer with a high degree of functionalization, this monomer must be introduced to a large extent. Must be used in large quantities. Furthermore, since it is a free radical polymerization, it is difficult to obtain a polymer with a wide molecular weight distribution and low viscosity.
「制御ラジカル重合法」は、更に、特定の官能基を有する連鎖移動剤を使用して重合を行うことにより末端に官能基を有するビニル系重合体が得られる「連鎖移動剤法」と、重合生長末端が停止反応等を起こさずに生長することによりほぼ設計どおりの分子量の重合体が得られる「リビングラジカル重合法」とに分類することができる。 The "controlled radical polymerization method" further includes the "chain transfer agent method" in which a vinyl polymer having a terminal functional group is obtained by polymerizing using a chain transfer agent having a specific functional group, and It can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing the growing end without causing a termination reaction or the like.
「連鎖移動剤法」は、官能化率の高い重合体を得ることが可能であるが、開始剤に対して特定の官能基を有する連鎖移動剤を必要とする。また上記の「一般的なラジカル重合法」と同様、フリーラジカル重合であるため分子量分布が広く、粘度の低い重合体は得にくい。 The "chain transfer agent method" makes it possible to obtain a polymer with a high degree of functionalization, but requires a chain transfer agent having a specific functional group for the initiator. Also, like the above-mentioned "general radical polymerization method", since it is a free radical polymerization, it has a wide molecular weight distribution and it is difficult to obtain a polymer with a low viscosity.
これらの重合法とは異なり、「リビングラジカル重合法」は、本件出願人自身の発明に係る国際公開ＷＯ９９／６５９６３号公報に記載されるように、重合速度が大きく、ラジカル同士のカップリング等による停止反応が起こりやすいため制御の難しいとされるラジカル重合でありながら、停止反応が起こりにくく、分子量分布の狭い、例えば、質量平均分子量Ｍｗと数平均分子量Ｍｎの比（Ｍｗ／Ｍｎ）が１．１～１．５程度の重合体が得られるとともに、モノマーと開始剤の仕込み比によって分子量は自由にコントロールすることができる。 Unlike these polymerization methods, the "living radical polymerization method" has a high polymerization rate and is based on coupling between radicals, etc., as described in International Publication No. WO 99/65963, which is an invention of the present applicant. Although radical polymerization is considered difficult to control because termination reactions are likely to occur, termination reactions are difficult to occur and the molecular weight distribution is narrow, for example, when the ratio of mass average molecular weight Mw to number average molecular weight Mn (Mw/Mn) is 1. A polymer with a molecular weight of about 1 to 1.5 can be obtained, and the molecular weight can be freely controlled by adjusting the charging ratio of monomer and initiator.
従って、「リビングラジカル重合法」は、分子量分布が狭く、粘度が低い重合体を得ることができる上に、特定の官能基を有するモノマーを重合体のほぼ任意の位置に導入することができるため、より好ましい重合法である。 Therefore, the "living radical polymerization method" can not only produce a polymer with a narrow molecular weight distribution and low viscosity, but also allow monomers with specific functional groups to be introduced into almost any position of the polymer. , is a more preferred polymerization method.
「リビングラジカル重合法」の中でも、有機ハロゲン化物あるいはハロゲン化スルホニル化合物等を開始剤、遷移金属錯体を触媒としてビニル系モノマーを重合する「原子移動ラジカル重合法」（Ａｔｏｍ Ｔｒａｎｓｆｅｒ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ：ＡＴＲＰ）は、上記の「リビングラジカル重合法」の特徴に加えて、官能基変換反応に比較的有利なハロゲン等を末端に有し、開始剤や触媒の設計の自由度が大きいことから、特定の官能基を有する上記マクロモノマーの製造方法としては更に好ましい。この原子移動ラジカル重合法としては例えばＭａｔｙｊａｓｚｅｗｓｋｉら、ジャーナル・オブ・アメリカン・ケミカルソサエティー（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）１９９５年、１１７巻、５６１４頁等が挙げられる。 Among the "living radical polymerization methods," the "atom transfer radical polymerization (ATRP)" method polymerizes vinyl monomers using an organic halide or halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst. In addition to the characteristics of the above-mentioned "living radical polymerization method," it has a terminal halogen etc. that is relatively advantageous for functional group conversion reactions, and has a high degree of freedom in designing the initiator and catalyst. The method for producing the above-mentioned macromonomer having the following is more preferable. Examples of this atom transfer radical polymerization method include Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.), 1995, vol. 117, p. 5614.
上記マクロモノマーの製法として、これらのうちどの方法を使用するかは特に制約はないが、通常、制御ラジカル重合法が利用され、更に制御の容易さ等からリビングラジカル重合法が好ましく用いられ、特に原子移動ラジカル重合法が最も好ましい。 There are no particular restrictions on which of these methods to use for producing the macromonomer, but controlled radical polymerization is usually used, and living radical polymerization is preferably used because of ease of control. Atom transfer radical polymerization is most preferred.
ランダム型グラフト共重合体用のマクロモノマーを原子移動ラジカル重合法により製造する場合、例えば、アクリロニトリル（ｂ１）とその他のエチレン性不飽和モノマー（ｂ２）とを用いたランダム共重合体を作製し、次いで、上記単独重合体又は共重合体の末端に、その他のエチレン性不飽和モノマー（ｂ２）を反応させ、最後に、得られた重合体の末端に、反応性官能基を導入することにより製造することができる。 When producing a macromonomer for a random graft copolymer by an atom transfer radical polymerization method, for example, a random copolymer using acrylonitrile (b1) and another ethylenically unsaturated monomer (b2) is produced, Next, the end of the homopolymer or copolymer is reacted with another ethylenically unsaturated monomer (b2), and finally, a reactive functional group is introduced into the end of the obtained polymer. can do.
ランダム型グラフト共重合体の製造方法としては、重合の簡便さ及び重合発熱の緩和の観点から、溶液重合が好ましい。 As a method for producing the random graft copolymer, solution polymerization is preferred from the viewpoint of simplicity of polymerization and mitigation of polymerization heat generation.
＜アクリル系樹脂組成物＞
本発明の１以上の実施形態において、ランダム型グラフト共重合体からなるアクリル系樹脂に、該アクリル系樹脂と相溶性を有する可塑剤を配合してアクリル系樹脂組成物として用いることができる。
<Acrylic resin composition>
In one or more embodiments of the present invention, an acrylic resin composed of a random graft copolymer can be used as an acrylic resin composition by blending a plasticizer that is compatible with the acrylic resin.
可塑剤としては、アクリル系樹脂と相溶性を有し、かつ、沸点が２００℃以上の有機化合物であればよく、特に限定されない。例えば、ジメチルスルホン、ジエチルスルホン、ジプロピルスルホン、ジブチルスルホン、ジフェニルスルホン、ビニルスルホン、エチルメチルスルホン、メチルフェニルスルホンメチルビニルスルホン、３－メチルスルホラン等のスルホン系化合物；ジプロピルスルホキシド、テトラメチレンスルホキシド、ジイソプロピルスルホキシド、メチルフェニルスルホキシド、ジブチルスルホキシド、ジイソブチルスルホキシド、ジ-ｐ－トリルスルホキシド、ジフェニルスルホキシド及びベンジルスルホキシド等のスルホキシド系化合物；乳酸ラクチド等のラクチド類；ピロリドン、Ｎ－ビニルピロリドン、ε－カプロラクタム及びＮ－メチルカプロラクタム等のラクタム類；γ－ブチロラクトン、γ－ヘキサラクトン、γ－ヘプタラクトン、γ－オクタラクトン、ε－カプロラクトン及びε-オクタラクトン等のラクトン類を用いることができる。また、可塑剤は、１種を単独で用いても良く、２種以上を組み合わせて用いてもよい。 The plasticizer is not particularly limited as long as it is an organic compound that is compatible with the acrylic resin and has a boiling point of 200° C. or higher. For example, sulfone compounds such as dimethylsulfone, diethylsulfone, dipropylsulfone, dibutylsulfone, diphenylsulfone, vinylsulfone, ethylmethylsulfone, methylphenylsulfone, methylvinylsulfone, and 3-methylsulfolane; dipropylsulfoxide, tetramethylene sulfoxide, Sulfoxide compounds such as diisopropylsulfoxide, methylphenylsulfoxide, dibutylsulfoxide, diisobutylsulfoxide, di-p-tolylsulfoxide, diphenylsulfoxide and benzylsulfoxide; lactides such as lactic acid lactide; pyrrolidone, N-vinylpyrrolidone, ε-caprolactam and N - Lactams such as methylcaprolactam; lactones such as γ-butyrolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, ε-caprolactone and ε-octalactone can be used. Moreover, one type of plasticizer may be used alone, or two or more types may be used in combination.
可塑剤は、繊維が該可塑剤の融点よりも高い温度で保持されたときに、液体となって繊維表面に滲み出てくる場合があるため、繊維の外観や触感を低下させ、その後室温（２５±５℃）に戻った際に固体となって繊維間が膠着する問題が発生し易くなる。特に海外輸送時には船内コンテナで６０℃まで室内温度の上がる場合があり、繊維加工時には短時間ではあるものの９０℃となることもあることから、前記アクリル系樹脂向け可塑剤の融点は６０℃以上であることが好ましく、より好ましくは９０℃以上である。例えば、ジメチルスルホン、乳酸ラクチド及びε－カプロラクタムからなる群から選ばれる１種以上を用いることが好ましく、ジメチルスルホン及び乳酸ラクチドからなる群から選ばれる１種以上を用いることがより好ましい。 Plasticizers may become liquid and ooze out onto the fiber surface when the fibers are held at a temperature higher than the melting point of the plasticizer, reducing the appearance and feel of the fibers, and then allowing the fibers to cool to room temperature ( When the temperature returns to 25±5° C.), it becomes solid and the problem of sticking between fibers is likely to occur. Particularly during overseas transportation, the indoor temperature in a ship container can rise to 60°C, and during fiber processing, it can reach 90°C, albeit for a short time. Therefore, the melting point of the plasticizer for acrylic resins is 60°C or higher. The temperature is preferably 90°C or higher, and more preferably 90°C or higher. For example, it is preferable to use one or more selected from the group consisting of dimethylsulfone, lactic acid lactide, and ε-caprolactam, and more preferably one or more selected from the group consisting of dimethylsulfone and lactic acid lactide.
アクリル系樹脂組成物は、溶融加工性の観点から、上記アクリル系樹脂１００質量部に対して、上記可塑剤を０．１質量部以上５０質量部以下含むことが好ましい。可塑剤の配合量が５０質量部以下であると、溶融加工性が良好であるとともに、溶融混練時の樹脂粘度が向上するため混練効率が向上する傾向となる。 From the viewpoint of melt processability, the acrylic resin composition preferably contains 0.1 parts by mass or more and 50 parts by mass or less of the plasticizer based on 100 parts by mass of the acrylic resin. When the blending amount of the plasticizer is 50 parts by mass or less, melt processability is good, and the resin viscosity during melt-kneading improves, so kneading efficiency tends to improve.
アクリル系樹脂組成物は、更に、熱安定性のため、安定剤を含んでもよい。安定剤としては、熱安定性を付与するものであればよく、特に限定されない。安定剤は、溶融加工性を向上しつつ、着色を抑制し、透明性を確保する観点から、エポキシ系熱安定剤、ハイドロタルサイト系熱安定剤、錫系熱安定剤、Ｃａ－Ｚｎ系熱安定剤、及びβ－ジケトン系熱安定剤からなる群から選択される少なくとも１種以上の安定剤であることが好ましい。安定剤は、１種を単独で用いても良く、２種以上を組み合わせて用いても良い。 The acrylic resin composition may further contain a stabilizer for thermal stability. The stabilizer is not particularly limited as long as it imparts thermal stability. Stabilizers include epoxy-based heat stabilizers, hydrotalcite-based heat stabilizers, tin-based heat stabilizers, and Ca-Zn-based heat stabilizers from the viewpoint of improving melt processability, suppressing coloration, and ensuring transparency. Preferably, the stabilizer is at least one kind selected from the group consisting of stabilizers and β-diketone thermal stabilizers. The stabilizers may be used alone or in combination of two or more.
アクリル系樹脂組成物は、アクリル系樹脂１００質量部に対して、安定剤を０．１質量部以上３０質量部以下含むことが好ましく、より好ましくは０．２質量部以上２０質量部以下含み、更に好ましくは０．５質量部以上１０質量部以下含む。０．１質量部以上であると、着色抑制効果が良好である。また、３０質量部以下であると、着色抑制効果が良好であるとともに、透明性を確保でき、かつアクリル系樹脂成形体の力学特性の低下が軽微となる。 The acrylic resin composition preferably contains 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.2 parts by mass or more and 20 parts by mass or less of a stabilizer, based on 100 parts by mass of the acrylic resin. More preferably, the content is 0.5 parts by mass or more and 10 parts by mass or less. When the amount is 0.1 part by mass or more, the effect of suppressing coloring is good. Further, when the amount is 30 parts by mass or less, the effect of suppressing coloring is good, transparency can be ensured, and the deterioration of the mechanical properties of the acrylic resin molded product is slight.
アクリル系樹脂組成物は、本発明の目的を損なわない範囲内で、アクリル系樹脂と加工機との摩擦、剪断による発熱の低減、流動性及び離型性の向上の観点から、滑剤を含んでもよい。滑剤としては、例えば、ステアリン酸モノグリセライド、及びステアリルステアレート等の脂肪酸エステル系滑剤、流動パラフィン、パラフィンワックス、及び合成ポリエチレンワックス等の炭化水素系滑剤、ステアリン酸等の脂肪酸系滑剤、ステアリルアルコール等の高級アルコール系滑剤、ステアリン酸アミド、オレイン酸アミド、及びエルカ酸アミド等の脂肪族アミド系滑剤、メチレンビスステアリン酸アミド、及びエチレンビスステアリン酸アミド等のアルキレン脂肪酸アミド系滑剤、ステアリン酸鉛、ステアリン酸亜鉛、ステアリン酸カルシウム、及びステアリン酸マグネシウム等の金属石鹸系滑剤等を用いることができる。これらは一種で用いてもよく、二種以上を組み合わせて用いてもよい。滑剤の添加量は、アクリル系樹脂１００質量部に対して、１０質量部以下にすればよい。 The acrylic resin composition may contain a lubricant from the viewpoint of reducing heat generation due to friction between the acrylic resin and the processing machine and shearing, and improving fluidity and mold releasability, within a range that does not impair the purpose of the present invention. good. Examples of lubricants include fatty acid ester lubricants such as stearic acid monoglyceride and stearyl stearate, hydrocarbon lubricants such as liquid paraffin, paraffin wax, and synthetic polyethylene wax, fatty acid lubricants such as stearic acid, and stearyl alcohol. Higher alcohol-based lubricants, aliphatic amide-based lubricants such as stearic acid amide, oleic acid amide, and erucic acid amide, alkylene fatty acid amide-based lubricants such as methylene bis-stearic acid amide and ethylene bis-stearic acid amide, lead stearate, and stearin. Metal soap lubricants such as acid zinc, calcium stearate, and magnesium stearate can be used. These may be used alone or in combination of two or more. The amount of the lubricant added may be 10 parts by mass or less per 100 parts by mass of the acrylic resin.
アクリル系樹脂組成物は、本発明の目的を損なわない範囲内で、モダクリル加工助剤等の加工助剤を含んでもよい。アクリル系樹脂組成物で繊維を構成する場合は、曳糸性を高める観点から、加工助剤として、（メタ）アクリレート系重合体及び／又はスチレン・アクリロニトリル共重合体を含むことが好ましい。（メタ）アクリレート系重合体としては、（メタ）アクリレートと、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、スチレン、酢酸ビニル、アクリロニトリル等の共重合成分との共重合体を用いることができる。また、（メタ）アクリレート系重合体としては、市販のもの、例えば、カネカ製の「カネエースＰＡ２０」、「カネエースＰＡ１０１」等を用いることができる。加工助剤の添加量は、アクリル系樹脂１００質量部に対して、１０質量部以下にすることができる。 The acrylic resin composition may contain a processing aid such as a modacrylic processing aid within a range that does not impair the object of the present invention. When the fiber is composed of an acrylic resin composition, it is preferable to include a (meth)acrylate polymer and/or a styrene-acrylonitrile copolymer as a processing aid from the viewpoint of improving spinnability. (Meth)acrylate polymers include (meth)acrylate and copolymerized components such as butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, vinyl acetate, acrylonitrile, etc. Polymers can be used. Furthermore, as the (meth)acrylate polymer, commercially available products such as "Kane Ace PA20" and "Kane Ace PA101" manufactured by Kaneka can be used. The amount of the processing aid added can be 10 parts by mass or less with respect to 100 parts by mass of the acrylic resin.
アクリル系樹脂組成物は、溶融状態で用いる、すなわち溶融物として用いることができる。上記熱アクリル系樹脂組成物を溶融混練することで、溶融物を得ることができる。溶融混練の方法は、特に限定されず、樹脂組成物を溶融混練する一般的な方法を用いることができる。 The acrylic resin composition can be used in a molten state, that is, as a melt. A melt can be obtained by melt-kneading the thermal acrylic resin composition. The melt-kneading method is not particularly limited, and a general method for melt-kneading resin compositions can be used.
上記で得られたアクリル系樹脂組成物を、所定の形状に加工することで成形体を得ることができる。成形方法は、特に限定されず、押出成形法、射出成形法、インサート成形法、サンドイッチ成形法、発泡成形法、プレス成形法、ブロー成形法、カレンダー成形法、回転成形法、スラッシュ成形法、ディップ成形法、キャスト成形法等が挙げられる。成形体としては、フィルム、プレート、繊維、押出成形体、射出成形体等が挙げられる。前記成形体は、発泡体でもよく、多孔質でもよい。本発明において、「フィルム」とは、厚みが２００μｍ以下の薄膜状で、かつ柔軟性を有するものをいい、「プレート」とは、厚みが２００μｍを超える薄膜状もしくは板状のもので、かつ柔軟性のないものをいう。 A molded article can be obtained by processing the acrylic resin composition obtained above into a predetermined shape. The molding method is not particularly limited, and may include extrusion molding, injection molding, insert molding, sandwich molding, foam molding, press molding, blow molding, calendar molding, rotational molding, slush molding, and dip molding. Examples include a molding method, a cast molding method, and the like. Examples of molded bodies include films, plates, fibers, extrusion molded bodies, and injection molded bodies. The molded body may be a foamed body or porous. In the present invention, a "film" refers to a thin film with a thickness of 200 μm or less and is flexible, and a "plate" refers to a thin film or plate with a thickness of more than 200 μm and is flexible. Refers to something without sex.
アクリル系樹脂組成物からアクリル系繊維を構成することができる。具体的には、上記アクリル系樹脂組成物（例えば、溶融混練後のペレット状のアクリル系樹脂組成物）を溶融紡糸することで、アクリル系繊維を得ることができる。まず、上記アクリル系樹脂組成物を溶融紡糸して繊維状の未延伸糸にする。具体的には、押出機、例えば、一軸押出機、異方向二軸押出機、コニカル二軸押出機にて溶融混練したアクリル系樹脂組成物の溶融混練物（ペレット状のアクリル系樹脂組成物）を、押出機にて紡糸ノズルから吐出し、加熱筒を通過させてアクリル系樹脂組成物の繊維化物を引取機で引取可能な温度以上に昇温した後、空冷、風冷等の手段でガラス転移点以下の温度に冷却しながら、引き取ることで未延伸糸を形成する。押出機は、例えば、１２０℃以上２００℃以下の温度範囲で運転することが好ましい。引取速度／吐出速度の比は、特に限定されないが、例えば、１倍以上１００倍以下の範囲となる速度比で引き取ることが好ましく、紡糸安定性の観点から５倍以上５０倍以下の範囲であることがより好ましい。紡糸ノズルの口径は、特に限定されないが、例えば、０．０５ｍｍ以上２ｍｍ以下であることが好ましく、０．１ｍｍ以上１ｍｍ以下であることがより好ましい。紡糸ノズルからの吐出物がメルトフラクチャーを発現しないノズル温度以上で押し出すことが好ましい。紡糸ノズルの温度は、１６０℃以上であることが好ましく、１７０℃以上であることがより好ましい。加熱筒の温度は、２００℃以上であることが好ましく、２３０℃以上であることがより好ましい。冷却温度は、空冷で－１９６℃以上４０℃以下であることが好ましく、より好ましくは０℃以上３０℃以下であり、水冷で５℃以上６０℃以下であることが好ましく、より好ましくは１０℃以上４０℃以下である。 Acrylic fibers can be constructed from an acrylic resin composition. Specifically, acrylic fibers can be obtained by melt-spinning the acrylic resin composition (for example, a pelletized acrylic resin composition after melt-kneading). First, the above-mentioned acrylic resin composition is melt-spun into a fibrous undrawn yarn. Specifically, a melt-kneaded product of an acrylic resin composition (pellet-shaped acrylic resin composition) melt-kneaded in an extruder, for example, a single-screw extruder, a twin-screw extruder in opposite directions, or a conical twin-screw extruder. is discharged from a spinning nozzle in an extruder, passed through a heating tube, and heated to a temperature higher than that at which the fiberized product of the acrylic resin composition can be taken up by a taking machine. An undrawn yarn is formed by drawing the yarn while cooling it to a temperature below the transition point. The extruder is preferably operated in a temperature range of, for example, 120°C or higher and 200°C or lower. The ratio of take-up speed/discharge speed is not particularly limited, but for example, it is preferable to take it at a speed ratio in the range of 1 time or more and 100 times or less, and from the viewpoint of spinning stability, it is in the range of 5 times or more and 50 times or less. It is more preferable. The diameter of the spinning nozzle is not particularly limited, but is preferably, for example, 0.05 mm or more and 2 mm or less, and more preferably 0.1 mm or more and 1 mm or less. It is preferable to extrude the material discharged from the spinning nozzle at a temperature higher than the nozzle temperature at which melt fracture does not occur. The temperature of the spinning nozzle is preferably 160°C or higher, more preferably 170°C or higher. The temperature of the heating cylinder is preferably 200°C or higher, more preferably 230°C or higher. The cooling temperature is preferably -196°C or more and 40°C or less for air cooling, more preferably 0°C or more and 30°C or less, and preferably 5°C or more and 60°C or less for water cooling, and more preferably 10°C. The temperature is above 40°C.
上記で得られた未延伸糸に、公知の方法で延伸処理、及び必要に応じて熱緩和処理を施こすことができる。例えば、人工毛髪として用いる場合は、単繊維繊度が２ｄｔｅｘ以上１００ｄｔｅｘ以下の繊維にすることが好ましい。延伸処理条件としては延伸処理温度７０℃以上１５０℃以下の乾熱雰囲気下で、延伸倍率は１．１倍以上６倍以下程度にすることが好ましく、１．５倍以上４．５倍以下程度であることが更に好ましい。延伸処理を施した繊維に熱緩和処理を施して、好ましくは１％以上５０％以下の緩和率で、より好ましくは５％以上４０％以下の緩和率で繊維を緩和処理することにより、熱収縮率を低下させることができる。また繊維表面の凹凸を整えて、人毛に類似したサラサラ触感とするためにも熱緩和処理が好ましい。また、未延伸糸又は延伸糸を水洗することで、繊度のコントロールを行なうことも可能である。 The undrawn yarn obtained above can be subjected to a drawing treatment by a known method and, if necessary, a thermal relaxation treatment. For example, when used as artificial hair, it is preferable to use fibers with a single fiber fineness of 2 dtex or more and 100 dtex or less. As for the stretching treatment conditions, it is preferable that the stretching treatment temperature is 70°C or more and 150°C or less in a dry heat atmosphere, and the stretching ratio is about 1.1 times or more and 6 times or less, and about 1.5 times or more and 4.5 times or less. It is more preferable that Heat shrinkage is achieved by subjecting the stretched fibers to thermal relaxation treatment, preferably at a relaxation rate of 1% to 50%, more preferably at a relaxation rate of 5% to 40%. rate can be reduced. Heat relaxation treatment is also preferred in order to smooth out the unevenness of the fiber surface and give it a smooth feel similar to human hair. Further, the fineness can also be controlled by washing the undrawn yarn or the drawn yarn with water.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されない。 Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
まず、各種測定方法及び評価方法を説明する。
（１）質量平均分子量及び数平均分子量
ゲル浸透クロマトグラフィー(東ソー社製の「ＨＬＣ－８３２０ＧＰＣ」)を用いて測定・算出した。
（２）貯蔵弾性率Ｇ’
動的粘弾性装置(ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製の「ＡＲＥＳ－Ｇ２」)を用いて、各実施例及び比較例で得られたグラフト共重合体について、６０℃及び１２０℃で、角周波数１ｒａｄ／ｓでの貯蔵弾性率Ｇ’を測定した。測定条件は以下のとおりである。
・モード：ねじりモード
・プレート径：８ｍｍφ
・歪み：０．０１％（２５℃）
（３）ガラス転移温度
示差走査熱量計（セイコーインスツルメンツ社製の「ＤＳＣ－６１００」）を用いて、各実施例及び比較例で得られたグラフト共重合体について、－８０℃から１６０℃まで２０℃／ｍｉｎで昇温した後に、再度－８０℃まで２０℃／ｍｉｎにて降温し、熱履歴を排除した上で、もう一度－８０℃から１６０℃へ１０℃／ｍｉｎで昇温することにより測定した。
First, various measurement methods and evaluation methods will be explained.
(1) Mass average molecular weight and number average molecular weight Measured and calculated using gel permeation chromatography (“HLC-8320GPC” manufactured by Tosoh Corporation).
(2) Storage modulus G'
Using a dynamic viscoelasticity device ("ARES-G2" manufactured by TA Instruments), the graft copolymers obtained in each example and comparative example were measured at 60°C and 120°C at an angular frequency of 1 rad/s. The storage modulus G' of the sample was measured. The measurement conditions are as follows.
・Mode: Torsion mode ・Plate diameter: 8mmφ
・Distortion: 0.01% (25℃)
(3) Glass transition temperature Using a differential scanning calorimeter ("DSC-6100" manufactured by Seiko Instruments), the graft copolymers obtained in each example and comparative example were measured from -80°C to 160°C for 20°C. After raising the temperature at a rate of ℃/min, the temperature is lowered again to -80℃ at a rate of 20℃/min, and after eliminating the thermal history, the temperature is raised again from -80℃ to 160℃ at a rate of 10℃/min. did.
［マクロモノマーの作製］
（製造例１）
反応容器に、アクリロニトリル０．８質量部、アクリル酸２―メトキシエチル３９．２質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル３．４３質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０１９７質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０２０３質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．０３１質量部及びトリエチルアミン０．０３６質量部をメタノール３．０質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から７０分後、反応容器内のモノマー消費率が３％（全モノマー消費率８％）に達した時に、アクリロニトリル１．３質量部、アクリル酸２－メトキシエチル５８．７質量部を７５分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の過熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から３１０分後、反応容器内のモノマー消費率が９５％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー１を得た。
[Preparation of macromonomer]
(Manufacturing example 1)
In a reaction vessel, 0.8 parts by mass of acrylonitrile, 39.2 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 3.43 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine were added. The charged raw materials were stirred at 40° C. under a nitrogen atmosphere. Subsequently, 0.0197 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol and added to 0.0203 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.031 parts by mass of ascorbic acid and 0.036 parts by mass of triethylamine were adjusted with 3.0 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 70 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 3% (total monomer consumption rate 8%), 1.3 parts by mass of acrylonitrile and 58.7 parts of 2-methoxyethyl acrylate were added. Parts by mass were added dropwise to the reaction system over 75 minutes. Thereafter, heating and stirring of the reaction solution was continued while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 310 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 95%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 1 with a Br group at one end.
フラスコに、片末端Ｂｒ基ポリマー１を１００質量部仕込み、ジメチルアセトアミド１００質量部で希釈し、そこへ、アクリル酸カリウム３．９質量部を加えて、７０℃で３時間加熱攪拌を行った。その後、反応混合物よりジメチルアセトアミドを留去し、反応混合物をトルエンに溶解させ、活性アルミナカラムを通したのち、トルエンを留去することにより、アクリロニトリルに由来する構成単位が均一に導入された片末端アクリロイル基マクロモノマー１を得た。得られた片末端アクリロイル基マクロモノマー１の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。なお、片末端アクリロイル基マクロモノマー１は、アクリロイル基末端とは反対側の末端を含み、かつ、片末端アクリロイル基マクロモノマー１中の全構成単位の数の半数の構成単位を含む末端領域中に、アクリロニトリルに由来する全構成単位の５１モル％を含む。 A flask was charged with 100 parts by mass of Polymer 1 having a Br group at one end, diluted with 100 parts by mass of dimethylacetamide, 3.9 parts by mass of potassium acrylate was added thereto, and the mixture was heated and stirred at 70° C. for 3 hours. Thereafter, dimethylacetamide was distilled off from the reaction mixture, the reaction mixture was dissolved in toluene, passed through an activated alumina column, and the toluene was distilled off, resulting in one end into which structural units derived from acrylonitrile were uniformly introduced. Acryloyl group macromonomer 1 was obtained. The number average molecular weight of the obtained macromonomer 1 having an acryloyl group at one end was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2. The macromonomer 1 with an acryloyl group at one end includes an end opposite to the end of the acryloyl group, and a terminal region containing half of the total number of structural units in the macromonomer 1 with an acryloyl group at one end. , containing 51 mol% of the total structural units derived from acrylonitrile.
（製造例２）
反応容器に、アクリロニトリル１．７質量部、アクリル酸２―メトキシエチル３８．３質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル３．５４質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０２０３質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０２０９質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．７９９質量部及びトリエチルアミン０．９１８質量部をメタノール１４．３質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から７０分後、反応容器内のモノマー消費率が６８％（全モノマー消費率２７％）に達した時に、アクリロニトリル２．６質量部、アクリル酸２－メトキシエチル５７．４質量部を７５分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の過熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から２４０分後、反応容器内のモノマー消費率が９７％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー２を得た。
(Manufacturing example 2)
In a reaction vessel, 1.7 parts by mass of acrylonitrile, 38.3 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 3.54 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine were added. The charged raw materials were stirred at 40° C. under a nitrogen atmosphere. Subsequently, 0.0203 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol and added to 0.0209 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.799 parts by mass of ascorbic acid and 0.918 parts by mass of triethylamine were adjusted with 14.3 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 70 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 68% (total monomer consumption rate 27%), 2.6 parts by mass of acrylonitrile and 57.4 parts of 2-methoxyethyl acrylate were added. Parts by mass were added dropwise to the reaction system over 75 minutes. Thereafter, heating and stirring of the reaction solution was continued while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 240 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 97%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 2 with a Br group at one end.
得られた片末端Ｂｒ基ポリマー２は、製造例１と同様にして、片末端アクリロイル基に変換し、アクリロニトリルに由来する構成単位が均一に導入された片末端アクリロイル基マクロモノマー２を得た。得られた片末端アクリロイル基マクロモノマー２の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。なお、片末端アクリロイル基マクロモノマー２は、アクリロイル基末端とは反対側の末端を含み、かつ、片末端アクリロイル基マクロモノマー２中の全構成単位の数の半数の構成単位を含む末端領域中に、アクリロニトリルに由来する全構成単位の５１モル％を含む。 The obtained polymer 2 having a Br group at one end was converted into an acryloyl group at one end in the same manner as in Production Example 1 to obtain a macromonomer 2 having an acryloyl group at one end into which structural units derived from acrylonitrile were uniformly introduced. The number average molecular weight of the obtained one-end acryloyl group macromonomer 2 was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2. In addition, the one-end acryloyl group macromonomer 2 includes an end opposite to the acryloyl group end, and has a terminal region containing half the number of structural units of the total number of structural units in the one-end acryloyl group macromonomer 2. , containing 51 mol% of the total structural units derived from acrylonitrile.
（製造例３）
反応容器に、アクリロニトリル３．７質量部、アクリル酸２―メトキシエチル３６．３質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル３．７８質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０２１６質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０２２３質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．８５３質量部及びトリエチルアミン０．９８０質量部をメタノール１５．２質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から７０分後、反応容器内のモノマー消費率が４４％（全モノマー消費率１８％）に達した時に、アクリロニトリル５．６質量部、アクリル酸２－メトキシエチル５４．４質量部を７５分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の過熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から３１０分後、反応容器内のモノマー消費率が９５％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー３を得た。
(Manufacturing example 3)
In a reaction vessel, 3.7 parts by mass of acrylonitrile, 36.3 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 3.78 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine were added. The charged raw materials were stirred at 40° C. under a nitrogen atmosphere. Subsequently, 0.0216 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol and added to 0.0223 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.853 parts by mass of ascorbic acid and 0.980 parts by mass of triethylamine were adjusted with 15.2 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 70 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 44% (total monomer consumption rate 18%), 5.6 parts by mass of acrylonitrile and 54.4 parts of 2-methoxyethyl acrylate were added. Parts by mass were added dropwise to the reaction system over 75 minutes. Thereafter, heating and stirring of the reaction solution was continued while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 310 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 95%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 3 with a Br group at one end.
得られた片末端Ｂｒ基ポリマー３は、製造例１と同様にして、片末端アクリロイル基に変換し、アクリロニトリルに由来する構成単位が均一に導入された片末端アクリロイル基マクロモノマー３を得た。得られた片末端アクリロイル基マクロモノマー３の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。なお、片末端アクリロイル基マクロモノマー３は、アクリロイル基末端とは反対側の末端を含み、かつ、片末端アクリロイル基マクロモノマー３中の全構成単位の数の半数の構成単位を含む末端領域中に、アクリロニトリルに由来する全構成単位の５２モル％を含む。 The obtained polymer 3 having a Br group at one end was converted into an acryloyl group at one end in the same manner as in Production Example 1 to obtain a macromonomer 3 having an acryloyl group at one end into which structural units derived from acrylonitrile were uniformly introduced. The number average molecular weight of the obtained macromonomer 3 having an acryloyl group at one end was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2. In addition, the one-end acryloyl group macromonomer 3 includes an end opposite to the acryloyl group end, and has a terminal region containing half the number of structural units of the total number of structural units in the one-end acryloyl group macromonomer 3. , containing 52 mol% of the total structural units derived from acrylonitrile.
（製造例４）
反応容器に、アクリロニトリル５．９質量部、アクリル酸２―メトキシエチル３４．１質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル４．０５質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０２３２質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０２３９質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．９１４質量部及びトリエチルアミン１．０５１質量部をメタノール１６．３質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から７０分後、反応容器内のモノマー消費率が１２％（全モノマー消費率５％）に達した時に、アクリロニトリル８．９質量部、アクリル酸２－メトキシエチル５１．１質量部を７５分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の過熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から３２０分後、反応容器内のモノマー消費率が９５％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー４を得た。
(Manufacturing example 4)
In a reaction vessel, 5.9 parts by mass of acrylonitrile, 34.1 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 4.05 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine were added. The charged raw materials were stirred at 40° C. under a nitrogen atmosphere. Subsequently, 0.0232 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol and added to 0.0239 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.914 parts by mass of ascorbic acid and 1.051 parts by mass of triethylamine were adjusted with 16.3 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 70 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 12% (total monomer consumption rate 5%), 8.9 parts by mass of acrylonitrile and 51.1 parts of 2-methoxyethyl acrylate were added. Parts by mass were added dropwise to the reaction system over 75 minutes. Thereafter, heating and stirring of the reaction solution was continued while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 320 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 95%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 4 with a Br group at one end.
得られた片末端Ｂｒ基ポリマー４は、製造例１と同様にして、片末端アクリロイル基に変換し、アクリロニトリルに由来する構成単位が均一に導入された片末端アクリロイル基マクロモノマー４を得た。得られた片末端アクリロイル基マクロモノマー４の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。なお、片末端アクリロイル基マクロモノマー４は、アクリロイル基末端とは反対側の末端を含み、かつ、片末端アクリロイル基マクロモノマー４中の全構成単位の数の半数の構成単位を含む末端領域中に、アクリロニトリルに由来する全構成単位の５３モル％を含む。 The obtained polymer 4 having a Br group at one end was converted to an acryloyl group at one end in the same manner as in Production Example 1 to obtain a macromonomer 4 having an acryloyl group at one end into which structural units derived from acrylonitrile were uniformly introduced. The number average molecular weight of the obtained macromonomer 4 having an acryloyl group at one end was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2. In addition, the one-end acryloyl group macromonomer 4 includes an end opposite to the acryloyl group end, and has a terminal region containing half of the total number of structural units in the one-end acryloyl group macromonomer 4. , containing 53 mol% of the total structural units derived from acrylonitrile.
（製造例５）
反応容器に、アクリロニトリル８．５質量部、アクリル酸２―メトキシエチル３１．５質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル４．３６質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０２５０質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０２５８質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．９８５質量部及びトリエチルアミン１．１３２質量部をメタノール１７．６質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から７０分後、反応容器内のモノマー消費率が２５％（全モノマー消費率１０％）に達した時に、アクリロニトリル１２．８質量部、アクリル酸２－メトキシエチル４７．２質量部を７５分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の過熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から３１０分後、反応容器内のモノマー消費率が９５％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー５を得た。
(Manufacturing example 5)
In a reaction vessel, 8.5 parts by mass of acrylonitrile, 31.5 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 4.36 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine were added. The charged raw materials were stirred at 40° C. under a nitrogen atmosphere. Subsequently, 0.0250 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol and added to 0.0258 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.985 parts by mass of ascorbic acid and 1.132 parts by mass of triethylamine were adjusted with 17.6 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 70 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 25% (total monomer consumption rate 10%), 12.8 parts by mass of acrylonitrile and 47.2 parts of 2-methoxyethyl acrylate were added. Parts by mass were added dropwise to the reaction system over 75 minutes. Thereafter, heating and stirring of the reaction solution was continued while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 310 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 95%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 5 with a Br group at one end.
得られた片末端Ｂｒ基ポリマー５は、製造例１と同様にして、片末端アクリロイル基に変換し、アクリロニトリルに由来する構成単位が均一に導入された片末端アクリロイル基マクロモノマー５を得た。得られた片末端アクリロイル基マクロモノマー５の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。なお、片末端アクリロイル基マクロモノマー５は、アクリロイル基末端とは反対側の末端を含み、かつ、片末端アクリロイル基マクロモノマー５中の全構成単位の数の半数の構成単位を含む末端領域中に、アクリロニトリルに由来する全構成単位の５３モル％を含む。 The obtained polymer 5 having a Br group at one end was converted to an acryloyl group at one end in the same manner as in Production Example 1 to obtain a macromonomer 5 having an acryloyl group at one end into which structural units derived from acrylonitrile were uniformly introduced. The number average molecular weight of the obtained macromonomer 5 having an acryloyl group at one end was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2. In addition, the one-end acryloyl group macromonomer 5 includes an end opposite to the acryloyl group end, and has a terminal region containing half of the total number of structural units in the one-end acryloyl group macromonomer 5. , containing 53 mol% of the total structural units derived from acrylonitrile.
（製造例６）
反応容器に、アクリル酸２－メトキシエチル４０質量部、メタノール（ＭｅＯＨ）１２質量部、２－ブロモ酪酸エチル３．３３質量部、及びトリエチルアミン０．１８質量部を仕込み、仕込んだ原料を窒素雰囲気下４０℃で攪拌した。続いて、臭化銅（ＩＩ）（ＣｕＢｒ２）０．０１９１質量部をメタノール８質量部で溶解させ、ヘキサメチルトリス（２－アミノエチル）アミン（Ｍｅ６ＴＲＥＮ）０．０１９７質量部に加えた後、反応系に添加し、反応系中の原料を混合した。更に、アスコルビン酸０．０１５質量部及びトリエチルアミン０．０１７質量部をメタノール３．０質量部で調整し、得られたアスコルビン酸溶液を反応系に滴下し、重合を開始とした。重合途中は、反応溶液の温度が４０～６０℃となるように、アスコルビン酸溶液の滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から６０分後、反応容器内のモノマー消費率が３７％（全モノマー消費率１５％）に達した時に、アクリル酸２―メトキシエチル６０質量部を６０分かけて反応系に滴下添加した。その後も反応容器の温度が４０℃～６０℃となるようにアスコルビン酸溶液の反応系への滴下速度を調整しながら反応溶液の加熱及び攪拌を続けた。アスコルビン酸溶液の滴下開始から３１０分後、反応容器内のモノマー消費率が９５％になり、アスコルビン酸の滴下を止めて反応終了とした。得られた反応物はトルエンで希釈し、活性アルミナカラムを通したのち、揮発分を減圧留去することにより、片末端Ｂｒ基ポリマー６を得た。
(Manufacturing example 6)
A reaction vessel was charged with 40 parts by mass of 2-methoxyethyl acrylate, 12 parts by mass of methanol (MeOH), 3.33 parts by mass of ethyl 2-bromobutyrate, and 0.18 parts by mass of triethylamine, and the charged raw materials were heated under a nitrogen atmosphere. The mixture was stirred at 40°C. Subsequently, 0.0191 parts by mass of copper(II) bromide (CuBr 2 ) was dissolved in 8 parts by mass of methanol, and added to 0.0197 parts by mass of hexamethyltris(2-aminoethyl)amine (Me 6 TREN). After that, it was added to the reaction system, and the raw materials in the reaction system were mixed. Furthermore, 0.015 parts by mass of ascorbic acid and 0.017 parts by mass of triethylamine were adjusted with 3.0 parts by mass of methanol, and the obtained ascorbic acid solution was dropped into the reaction system to initiate polymerization. During the polymerization, the reaction solution was heated and stirred while adjusting the dropping rate of the ascorbic acid solution so that the temperature of the reaction solution was 40 to 60°C. 60 minutes after the start of dropping the ascorbic acid solution, when the monomer consumption rate in the reaction vessel reached 37% (total monomer consumption rate 15%), 60 parts by mass of 2-methoxyethyl acrylate was added to the reaction system over 60 minutes. was added dropwise. Thereafter, the reaction solution was continued to be heated and stirred while adjusting the dropping rate of the ascorbic acid solution into the reaction system so that the temperature of the reaction vessel was 40°C to 60°C. 310 minutes after the start of dropwise addition of the ascorbic acid solution, the monomer consumption rate in the reaction vessel reached 95%, and the dropwise addition of ascorbic acid was stopped to conclude the reaction. The obtained reaction product was diluted with toluene, passed through an activated alumina column, and volatile components were distilled off under reduced pressure to obtain a polymer 6 with a Br group at one end.
得られた片末端Ｂｒ基ポリマー６は、製造例１と同様にして、片末端アクリロイル基に変換し、アクリロニトリルに由来する構成単位が含まれない片末端アクリロイル基マクロモノマー６を得た。得られた片末端アクリロイル基マクロモノマー６の数平均分子量は６０００であり、分子量分布（質量平均分子量／数平均分子量）は１．２であった。 The obtained polymer 6 having a Br group at one end was converted to an acryloyl group at one end in the same manner as in Production Example 1, to obtain a macromonomer 6 having an acryloyl group at one end and containing no structural unit derived from acrylonitrile. The number average molecular weight of the obtained macromonomer 6 having an acryloyl group at one end was 6,000, and the molecular weight distribution (mass average molecular weight/number average molecular weight) was 1.2.
［グラフト共重合体の作製］
（実施例１）
重合反応器内に、酢酸ビニル６６．５質量部、アクリロニトリル６．７質量部、製造例１で得られた片末端アクリロイル基マクロモノマー１を５質量部、ジメチルアセトアミド４０質量部、２，２’－アゾビス（２－メチルブチルロニトリル）１．３５質量部を仕込んだ後、１５分間窒素雰囲気下で攪拌した。その後、重合反応器を７０℃に上昇させて重合を開始した。昇温開始から３０分後、アクリロニトリル２６．８部を７時間一定の速度で連続的に添加した。アクリロニトリルの滴下終了から３０分後（昇温開始から８時間後）まで溶液重合を行った。得られた重合物を、熱風乾燥機にて５０℃で３時間乾燥し、更に真空乾燥機にて１２０℃で１２時間乾燥して、グラフト共重合体１を得た。得られたグラフト共重合体１は、酢酸ビニルに由来する構成単位が５８．７質量％、アクリロニトリルに由来する構成単位が３５．５質量％、片末端マクロモノマーに由来する構成単位が５．８質量％で、質量平均分子量は約２８０００であった。
[Preparation of graft copolymer]
(Example 1)
In a polymerization reactor, 66.5 parts by mass of vinyl acetate, 6.7 parts by mass of acrylonitrile, 5 parts by mass of the one-end acryloyl group macromonomer 1 obtained in Production Example 1, 40 parts by mass of dimethylacetamide, 2,2' - After 1.35 parts by mass of azobis(2-methylbutylronitrile) was charged, the mixture was stirred for 15 minutes under a nitrogen atmosphere. Thereafter, the temperature of the polymerization reactor was raised to 70°C to start polymerization. Thirty minutes after the start of temperature rise, 26.8 parts of acrylonitrile was continuously added at a constant rate for 7 hours. Solution polymerization was carried out until 30 minutes after the end of the dropwise addition of acrylonitrile (8 hours after the start of temperature rise). The obtained polymer was dried in a hot air dryer at 50°C for 3 hours, and further dried in a vacuum dryer at 120°C for 12 hours to obtain Graft Copolymer 1. The obtained graft copolymer 1 contained 58.7% by mass of constitutional units derived from vinyl acetate, 35.5% by mass of constitutional units derived from acrylonitrile, and 5.8% by mass of constitutional units derived from one end macromonomer. The weight average molecular weight in weight percent was about 28,000.
（実施例２）
製造例１で得られた片末端アクリロイル基マクロモノマー１に代えて製造例２で得られた片末端アクリロイル基マクロモノマー２を用いたこと以外は、実施例１と同様にしてグラフト共重合体２を得た。得られたグラフト共重合体２は、酢酸ビニルに由来する構成単位が５９．７質量％、アクリロニトリルに由来する構成単位が３４．７質量％、片末端マクロモノマーに由来する構成単位が５．６質量％で、質量平均分子量は約３１０００であった。
(Example 2)
Graft copolymer 2 was prepared in the same manner as in Example 1, except that macromonomer 2 with an acryloyl group on one end obtained in Production Example 2 was used in place of macromonomer 1 with an acryloyl group on one end obtained in Production Example 1. I got it. The obtained graft copolymer 2 contained 59.7% by mass of structural units derived from vinyl acetate, 34.7% by mass of structural units derived from acrylonitrile, and 5.6% by mass of structural units derived from one-end macromonomer. The weight average molecular weight in weight percent was about 31,000.
（実施例３）
製造例１で得られた片末端アクリロイル基マクロモノマー１に代えて製造例３で得られた片末端アクリロイル基マクロモノマー３を用いたこと以外は、実施例１と同様にしてグラフト共重合体３を得た。得られたグラフト共重合体３は、酢酸ビニルに由来する構成単位が６０．１質量％、アクリロニトリルに由来する構成単位が３４．２質量％、片末端マクロモノマーに由来する構成単位が５．７質量％で、質量平均分子量は約２６０００であった。
(Example 3)
Graft copolymer 3 was prepared in the same manner as in Example 1, except that macromonomer 3 with an acryloyl group at one end obtained in Production Example 3 was used in place of macromonomer 1 with an acryloyl group at one end obtained in Production Example 1. I got it. The resulting graft copolymer 3 contained 60.1% by mass of constitutional units derived from vinyl acetate, 34.2% by mass of constitutional units derived from acrylonitrile, and 5.7% by mass of constitutional units derived from one-end macromonomer. The weight average molecular weight in weight percent was about 26,000.
（実施例４）
製造例１で得られた片末端アクリロイル基マクロモノマー１に代えて製造例４で得られた片末端アクリロイル基マクロモノマー４を用いたこと以外は、実施例１と同様にしてグラフト共重合体４を得た。得られたグラフト共重合体４は、酢酸ビニルに由来する構成単位が５７．４質量％、アクリロニトリルに由来する構成単位が３６．８質量％、片末端マクロモノマーに由来する構成単位が５．８質量％で、質量平均分子量は約２８０００であった。
(Example 4)
Graft copolymer 4 was prepared in the same manner as in Example 1, except that macromonomer 4 with an acryloyl group at one end obtained in Production Example 4 was used in place of macromonomer 1 with an acryloyl group at one end obtained in Production Example 1. I got it. The obtained graft copolymer 4 contained 57.4% by mass of constitutional units derived from vinyl acetate, 36.8% by mass of constitutional units derived from acrylonitrile, and 5.8% by mass of constitutional units derived from one-end macromonomer. The weight average molecular weight in weight percent was about 28,000.
（実施例５）
製造例１で得られた片末端アクリロイル基マクロモノマー１に代えて製造例５で得られた片末端アクリロイル基マクロモノマー５を用いたこと以外は、実施例１と同様にしてグラフト共重合体５を得た。得られたグラフト共重合体５は、酢酸ビニルに由来する構成単位が５６．５質量％、アクリロニトリルに由来する構成単位が３７．８質量％、片末端マクロモノマーに由来する構成単位が５．７質量％で、質量平均分子量は約２７０００であった。
(Example 5)
Graft copolymer 5 was prepared in the same manner as in Example 1, except that macromonomer 5 with an acryloyl group at one end obtained in Production Example 5 was used in place of macromonomer 1 with an acryloyl group at one end obtained in Production Example 1. I got it. The obtained graft copolymer 5 contained 56.5% by mass of constitutional units derived from vinyl acetate, 37.8% by mass of constitutional units derived from acrylonitrile, and 5.7% by mass of constitutional units derived from one end macromonomer. The weight average molecular weight in weight percent was about 27,000.
（比較例１）
製造例１で得られた片末端アクリロイル基マクロモノマー１に代えて製造例６で得られた片末端アクリロイル基マクロモノマー６を用いたこと以外は、実施例１と同様にしてグラフト共重合体６を得た。得られたグラフト共重合体６は、酢酸ビニルに由来する構成単位が５９．３質量％、アクリロニトリルに由来する構成単位が３５．２質量％、片末端マクロモノマーに由来する構成単位が５．６質量％で、質量平均分子量は約３００００であった。
(Comparative example 1)
Graft copolymer 6 was prepared in the same manner as in Example 1, except that macromonomer 6 with an acryloyl group at one end obtained in Production Example 6 was used in place of macromonomer 1 with an acryloyl group at one end obtained in Production Example 1. I got it. The obtained graft copolymer 6 contained 59.3% by mass of constitutional units derived from vinyl acetate, 35.2% by mass of constitutional units derived from acrylonitrile, and 5.6% by mass of constitutional units derived from one-end macromonomer. The weight average molecular weight in weight percent was about 30,000.
実施例１～５、及び比較例１で得られたグラフト共重合体の貯蔵弾性率を上述したとおりに評価し、その結果を下記表１に示した。なお、表１に記載された「ＡＮ」は、アクリロニトリルを意味する。 The storage modulus of the graft copolymers obtained in Examples 1 to 5 and Comparative Example 1 was evaluated as described above, and the results are shown in Table 1 below. In addition, "AN" described in Table 1 means acrylonitrile.
表１の結果から、枝ポリマーにアクリロニトリルを導入していない比較例１のグラフト共重合体と比較して、
（１）枝ポリマーに枝ポリマーの全構成単位に対し５モル％又は１０モル％のアクリロニトリルをランダムに導入した実施例１及び２のグラフト共重合体では、１２０℃での貯蔵弾性率が低下し、流動性が高くなり、
（２）枝ポリマーに枝ポリマーの全構成単位に対し２０モル％又は３０モル％のアクリロニトリルをランダムに導入した実施例３及び４のグラフト共重合体では、６０℃での貯蔵弾性率が向上し、強度が高くなるとともに、１２０℃での貯蔵弾性率が低下し、流動性が高くなり、
（３）枝ポリマーに枝ポリマーの全構成単位に対し４０モル％のアクリロニトリルをランダムに導入した実施例５のグラフト共重合体では、６０℃での貯蔵弾性率が向上し、強度が高くなる
ことが分かった。
これらの実験結果から、枝ポリマーにアクリロニトリルをランダムに導入することで、アクリロニトリルの導入量に応じて、強度及び流動性の一方又は両方の向上といった特性を付与することが可能となった。
From the results in Table 1, compared to the graft copolymer of Comparative Example 1 in which acrylonitrile was not introduced into the branch polymer,
(1) In the graft copolymers of Examples 1 and 2 in which 5 mol% or 10 mol% of acrylonitrile was randomly introduced into the branch polymer based on the total constituent units of the branch polymer, the storage modulus at 120°C decreased. , liquidity becomes higher;
(2) In the graft copolymers of Examples 3 and 4, in which 20 mol% or 30 mol% of acrylonitrile was randomly introduced into the branch polymer based on the total constituent units of the branch polymer, the storage modulus at 60°C was improved. , the strength increases, the storage modulus at 120°C decreases, the fluidity increases,
(3) In the graft copolymer of Example 5, in which 40 mol% of acrylonitrile was randomly introduced into the branch polymer based on the total constituent units of the branch polymer, the storage modulus at 60°C improved and the strength increased. I understand.
From these experimental results, by randomly introducing acrylonitrile into a branched polymer, it became possible to impart properties such as improved strength and fluidity, or both, depending on the amount of acrylonitrile introduced.
Claims (4)
アクリロニトリル（ｂ１）に由来する構成単位及びその他のエチレン性不飽和モノマー（ｂ２）に由来する構成単位を含む重合体からなる枝ポリマー（Ｂ）と、を含み、
前記枝ポリマー（Ｂ）は、第１の末端と第２の末端とを有し、前記第２の末端で前記幹ポリマー（Ａ）にグラフトしている、グラフト共重合体であって、
前記枝ポリマー（Ｂ）は、前記第１の末端を含み、かつ、前記枝ポリマー（Ｂ）中の全構成単位の数の半数の構成単位を含む末端領域中に、前記アクリロニトリル（ｂ１）に由来する全構成単位の３０モル％超７０モル％未満を含み、
前記アクリロニトリル（ｂ１）に由来する構成単位の含有量が、前記枝ポリマー（Ｂ）中の全構成単位に対し、３モル％以上５０モル％以下である、グラフト共重合体。 A backbone polymer (A) made of an acrylic resin containing a structural unit derived from acrylonitrile (a1) and a structural unit derived from another ethylenically unsaturated monomer (a2),
A branched polymer (B) consisting of a polymer containing a structural unit derived from acrylonitrile (b1) and a structural unit derived from another ethylenically unsaturated monomer (b2),
The branch polymer (B) is a graft copolymer having a first end and a second end, and is grafted to the trunk polymer (A) at the second end,
The branched polymer (B) contains a compound derived from the acrylonitrile (b1) in the terminal region that includes the first end and contains half the number of structural units of the total number of structural units in the branched polymer (B). Containing more than 30 mol% and less than 70 mol% of all structural units,
A graft copolymer in which the content of structural units derived from the acrylonitrile (b1) is 3 mol% or more and 50 mol% or less based on all the structural units in the branch polymer (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022046330A JP2023140475A (en) | 2022-03-23 | 2022-03-23 | graft copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022046330A JP2023140475A (en) | 2022-03-23 | 2022-03-23 | graft copolymer |
Publications (1)
| Publication Number | Publication Date |
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| JP2023140475A true JP2023140475A (en) | 2023-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2022046330A Pending JP2023140475A (en) | 2022-03-23 | 2022-03-23 | graft copolymer |
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| JP (1) | JP2023140475A (en) |
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2022
- 2022-03-23 JP JP2022046330A patent/JP2023140475A/en active Pending
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