JP6633774B2 - 変性共役ジエン系重合体およびその製造方法 - Google Patents
変性共役ジエン系重合体およびその製造方法 Download PDFInfo
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- JP6633774B2 JP6633774B2 JP2018552625A JP2018552625A JP6633774B2 JP 6633774 B2 JP6633774 B2 JP 6633774B2 JP 2018552625 A JP2018552625 A JP 2018552625A JP 2018552625 A JP2018552625 A JP 2018552625A JP 6633774 B2 JP6633774 B2 JP 6633774B2
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- 229920000642 polymer Polymers 0.000 title claims description 75
- 150000001993 dienes Chemical class 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000005842 heteroatom Chemical group 0.000 claims description 31
- 125000004434 sulfur atom Chemical group 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 15
- -1 naphthyl sodium Chemical compound 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- ZWPUOFSQNASCII-UHFFFAOYSA-N 1-(2-ethoxyethoxy)butane Chemical group CCCCOCCOCC ZWPUOFSQNASCII-UHFFFAOYSA-N 0.000 claims description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 claims 1
- ZATOFRITFRPYBT-UHFFFAOYSA-N C1=CC=C2C([Li])=CC=CC2=C1 Chemical compound C1=CC=C2C([Li])=CC=CC2=C1 ZATOFRITFRPYBT-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- NRUBUZBAZRTHHX-UHFFFAOYSA-N lithium;propan-2-ylazanide Chemical compound [Li+].CC(C)[NH-] NRUBUZBAZRTHHX-UHFFFAOYSA-N 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 description 52
- 239000005060 rubber Substances 0.000 description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- 239000000377 silicon dioxide Substances 0.000 description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 244000043261 Hevea brasiliensis Species 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- 239000011256 inorganic filler Substances 0.000 description 8
- 229910003475 inorganic filler Inorganic materials 0.000 description 8
- 229920003052 natural elastomer Polymers 0.000 description 8
- 229920001194 natural rubber Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000010734 process oil Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- 125000001424 substituent group Chemical group 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical group OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- 235000014692 zinc oxide Nutrition 0.000 description 2
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- 238000011925 1,2-addition Methods 0.000 description 1
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- CSBDTEMAXHVRBB-UHFFFAOYSA-N 2-ethoxy-n,n-dimethylethanamine Chemical compound CCOCCN(C)C CSBDTEMAXHVRBB-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003557 thiazoles Chemical class 0.000 description 1
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- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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- C08F236/06—Butadiene
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- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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Description
実施例1
20Lのオートクレーブ反応器に、スチレン270g、1,3‐ブタジエン710g、およびノルマルヘキサン5,000g、極性添加剤としてDTP(2,2‐ジ(2‐テトラヒドロフリル)プロパン)0.86gを入れた後、反応器の内部温度を40℃に昇温した。次に、n‐ブチルリチウム10mmolを反応器に投入し、断熱昇温反応を進行させた。断熱昇温反応が終わってから20分程度経過した後、1,3‐ブタジエン20gを投入して重合体の末端をブタジエンでキャッピング(capping)した。5分後、下記化学式1‐1で表される化合物0.5g(5mmol)を投入し、15分間反応させた。その後、エタノールを用いて重合反応を停止させ、酸化防止剤であるBHT(butylated hydroxytoluene)がヘキサンに0.3重量%溶解されている溶液45mlを添加した。その結果として得られた重合物をスチームで加熱された温水に入れ、撹拌して溶媒を除去した後、ロール乾燥して残量の溶媒と水を除去することで、変性共役ジエン系重合体を製造した。このように製造された変性共役ジエン系重合体に対する分析結果は、下記表1に示した。
前記実施例1において、前記化学式1‐1で表される化合物の代わりに、下記化学式1‐2で表される化合物を0.5g(5mmol)投入したことを除き、前記実施例1と同様の方法により実施した。
前記実施例1において、前記化学式1‐1で表される化合物を投入していないことを除き、前記実施例1と同様の方法により実施した。
前記実施例1において、前記化学式1‐1で表される化合物の代わりに、下記化学式6で表される化合物を0.5g(5mmol)投入したことを除き、前記実施例1と同様の方法により実施した。
実験例1
前記実施例および比較例で製造された各変性または未変性の共役ジエン系重合体に対して、重量平均分子量(Mw、X103g/mol)、数平均分子量(Mn、X103g/mol)、分子量分布(MWD)、およびムーニー粘度(MV)をそれぞれ測定した。結果を下記表1に示した。
前記実施例および比較例で製造された各変性または未変性の共役ジエン系共重合体を含むゴム組成物、およびそれから製造された成形品の物性を比較分析するために、引張特性、耐磨耗性、およびウェットグリップ性をそれぞれ測定し、その結果を下記表3に示した。
実施例および比較例の各変性または未変性のスチレン‐ブタジエン共重合体を原料ゴムとして、下記表2に示した配合条件で配合した。表2中の原料は、ゴム100重量部を基準とした各重量部である。
引張特性は、ASTM412の引張試験法に準じて各試験片を製造し、前記試験片の切断時における引張強度および300%伸び時の引張応力(300%モジュラス)を測定した。具体的に、引張特性は、Universal Test Machin 4204(Instron社製)引張試験機を用いて、室温で50cm/minの速度で測定した。
粘弾性特性は、動的機械分析機(TA社製)を用い、歪みモードで、周波数10Hz、各測定温度(−60℃〜60℃)で変形を変化させながらtanδを測定した。ペイン効果(Payne effect)は、変形0.28%〜40%での最小値と最大値の差で示した。低温0℃でのtanδが高いほど、ウェットグリップ性に優れることを意味し、高温60℃でのtanδが低いほど、ヒステリシス損が少なく、低走行抵抗性(燃費性)に優れることを意味する。
Claims (13)
- 共役ジエン系単量体由来の繰り返し単位を含み、かつ、一方の末端に、下記化学式1で表される化合物を含む変性剤由来の官能基を含む、変性共役ジエン系重合体。
(前記化学式1中、
nは3であり、
X1およびX2は、それぞれ独立して、N原子またはCR7であって、X1およびX2の必ず1つ以上はN原子であり、
R1〜R4は、それぞれ独立して、炭素数1〜30の2価の炭化水素基、またはN、O、およびS原子からなる群から選択される1つ以上のヘテロ原子を含む炭素数1〜30のヘテロアルキレン基であり、
R5およびR6は、それぞれ独立して、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1つ以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1つ以上のヘテロ原子を含む炭素数1〜30のヘテロ環基であり、
R7は、水素原子、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1つ以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1つ以上のヘテロ原子を含む炭素数1〜30のヘテロ環基である。) - 共役ジエン系単量体由来の繰り返し単位を含み、かつ、一方の末端に、下記化学式1で表される化合物を含み、かつ、他方の末端に、下記化学式2で表される化合物を含む変性開始剤由来の官能基を含む、変性共役ジエン系重合体。
(前記化学式1中、
nは3であり、
X1およびX2は、それぞれ独立して、N原子またはCR7であって、X1およびX2の必ず1つ以上はN原子であり、
R1〜R4は、それぞれ独立して、炭素数1〜30の2価の炭化水素基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキレン基であり、
R5およびR6は、それぞれ独立して、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基であり、
R7は、水素原子、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基であり、
前記化学式2中、
R8およびR9は、それぞれ独立して、炭素数1〜20のアルキル基、炭素数3〜20のシクロアルキル基、および炭素数5〜20のアラルキル基からなる群から選択される1種であるか、R8およびR9が互いに結合し、隣接したN原子とともに炭素数5〜20の飽和または不飽和の環状構造を形成し、前記R8およびR9が環状構造を形成する場合、分岐構造を有してもよく、
R10は、単結合、炭素数1〜20のアルキレン基、または下記式3〜5からなる群から選択される1種の連結基であり、
Mはアルカリ金属である。)
- 前記変性共役ジエン系重合体は、芳香族ビニル単量体由来の繰り返し単位をさらに含む、請求項1または2に記載の変性共役ジエン系重合体。
- 前記化学式1中、
X1およびX2はN原子であり、
R1〜R4は、それぞれ独立して、炭素数1〜10の2価の炭化水素基であり、
R5およびR6は、それぞれ独立して、炭素数1〜10の1価の炭化水素基である、請求項1〜3のいずれか一項に記載の変性共役ジエン系重合体。 - 前記化学式1で表される化合物が、下記化学式1‐1または1‐2で表される化合物である、請求項1〜4のいずれか一項に記載の変性共役ジエン系重合体。
(前記化学式1‐1および1‐2中、Meはメチル基であり、Etはエチル基である。) - 前記変性共役ジエン系重合体は、数平均分子量(Mn)が10,000g/mol〜2,000,000g/molである、請求項1〜5のいずれか一項に記載の変性共役ジエン系重合体。
- 分子量分布(Mw/Mn)が1〜5である、請求項1〜6のいずれか一項に記載の変性共役ジエン系重合体。
- 有機金属化合物を含む炭化水素溶媒中で、共役ジエン系単量体、または芳香族ビニル系単量体および共役ジエン系単量体を重合することで、有機金属が結合された活性重合体を製造するステップ(S1)と、
前記活性重合体と、下記化学式1で表される化合物を含む変性剤とを反応させるステップ(S2)と、を含む、変性共役ジエン系重合体の製造方法。
(前記化学式1中、
nは3であり、
X1およびX2は、それぞれ独立して、N原子またはCR7であって、X1およびX2の必ず1つ以上はN原子であり、
R1〜R4は、それぞれ独立して、炭素数1〜30の2価の炭化水素基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキレン基であり、
R5およびR6は、それぞれ独立して、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基であり、
R7は、水素原子、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基である。) - 前記有機金属化合物は、単量体の総量100gを基準として、0.01mmol〜10mmolで用いられる、請求項8に記載の変性共役ジエン系重合体の製造方法。
- 前記有機金属化合物が、メチルリチウム、エチルリチウム、プロピルリチウム、n‐ブチルリチウム、s‐ブチルリチウム、t‐ブチルリチウム、ヘキシルリチウム、n‐デシルリチウム、t‐オクチルリチウム、フェニルリチウム、1‐ナフチルリチウム、n‐エイコシルリチウム、4‐ブチルフェニルリチウム、4‐トリルリチウム、シクロヘキシルリチウム、3,5‐ジ‐n‐ヘプチルシクロヘキシルリチウム、4‐シクロペンチルリチウム、ナフチルナトリウム、ナフチルカリウム、リチウムアルコキシド、ナトリウムアルコキシド、カリウムアルコキシド、リチウムスルホネート、ナトリウムスルホネート、カリウムスルホネート、リチウムアミド、ナトリウムアミド、カリウムアミド、およびリチウムイソプロピルアミドからなる群から選択される1つ以上である、請求項8または9に記載の変性共役ジエン系重合体の製造方法。
- 前記(S1)ステップにおける重合は、極性添加剤を含んで行う、請求項8〜10のいずれか一項に記載の変性共役ジエン系重合体の製造方法。
- 前記極性添加剤が、テトラヒドロフラン、ジテトラヒドロフリルプロパン、ジエチルエーテル、シクロアミルエーテル、ジプロピルエーテル、エチレンジメチルエーテル、ジエチルグリコール、ジメチルエーテル、3級ブトキシエトキシエタン、ビス(3‐ジメチルアミノエチル)エーテル、(ジメチルアミノエチル)エチルエーテル、トリメチルアミン、トリエチルアミン、トリプロピルアミン、およびテトラメチルエチレンジアミンからなる群から選択される1つ以上である、請求項11に記載の変性共役ジエン系重合体の製造方法。
- 下記化学式1で表される化合物を含む変性剤。
(前記化学式1中、
nは3であり、
X1およびX2は、それぞれ独立して、N原子またはCR7であって、X1およびX2の必ず1つ以上はN原子であり、
R1〜R4は、それぞれ独立して、炭素数1〜30の2価の炭化水素基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキレン基であり、
R5およびR6は、それぞれ独立して、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基であり、
R7は、水素原子、炭素数1〜30の1価の炭化水素基、N、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロアルキル基、またはN、O、およびS原子からなる群から選択される1種以上のヘテロ原子を含む炭素数1〜30のヘテロ環基である。)
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