JP6468283B2 - 変性共役ジエン系ゴムの製造方法 - Google Patents
変性共役ジエン系ゴムの製造方法 Download PDFInfo
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- JP6468283B2 JP6468283B2 JP2016511616A JP2016511616A JP6468283B2 JP 6468283 B2 JP6468283 B2 JP 6468283B2 JP 2016511616 A JP2016511616 A JP 2016511616A JP 2016511616 A JP2016511616 A JP 2016511616A JP 6468283 B2 JP6468283 B2 JP 6468283B2
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- conjugated diene
- rubber
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- 238000000034 method Methods 0.000 title claims description 26
- 230000008569 process Effects 0.000 title description 6
- 229920001971 elastomer Polymers 0.000 claims description 112
- 239000005060 rubber Substances 0.000 claims description 112
- 150000001993 dienes Chemical class 0.000 claims description 65
- 229920000642 polymer Polymers 0.000 claims description 58
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- 238000004519 manufacturing process Methods 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 40
- 238000004132 cross linking Methods 0.000 claims description 33
- -1 diene compound Chemical class 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 26
- 239000003505 polymerization initiator Substances 0.000 claims description 15
- 239000012442 inert solvent Substances 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 3
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 229910052710 silicon Inorganic materials 0.000 description 3
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- 150000003512 tertiary amines Chemical class 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-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
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
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- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- 238000013329 compounding Methods 0.000 description 2
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- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
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- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
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- ZXZSYHLGFSXNNU-UHFFFAOYSA-N [[methyl(4-trimethoxysilylbutyl)carbamothioyl]trisulfanyl] N-methyl-N-(4-trimethoxysilylbutyl)carbamodithioate Chemical compound CO[Si](CCCCN(C(=S)SSSSC(N(C)CCCC[Si](OC)(OC)OC)=S)C)(OC)OC ZXZSYHLGFSXNNU-UHFFFAOYSA-N 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
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- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
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- SLPLCLDJTNLWPW-UHFFFAOYSA-N barium(2+);2-methylpropan-2-olate Chemical compound [Ba+2].CC(C)(C)[O-].CC(C)(C)[O-] SLPLCLDJTNLWPW-UHFFFAOYSA-N 0.000 description 1
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- ICKUIYZTJRDAPK-UHFFFAOYSA-N naphthalene;potassium Chemical class [K].[K].C1=CC=CC2=CC=CC=C21 ICKUIYZTJRDAPK-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- SGAOTOMUHFNBAR-UHFFFAOYSA-N strontium;2-methylpropan-2-olate Chemical compound [Sr+2].CC(C)(C)[O-].CC(C)(C)[O-] SGAOTOMUHFNBAR-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
Description
本発明の変性共役ジエン系ゴムの製造方法は、不活性溶媒中で、重合開始剤を用いて、少なくとも共役ジエン化合物を含んでなる単量体を重合し、活性末端を有する共役ジエン系重合体を得る第1工程と、前記活性末端を有する共役ジエン系重合体の活性末端に、後述する式(1)で表される化合物を反応させる第2工程と、を備える。
まず、本発明の製造方法における第1工程について説明する。本発明の製造方法における第1工程は、不活性溶媒中で、重合開始剤を用いて、少なくとも共役ジエン化合物を含んでなる単量体を重合し、活性末端を有する共役ジエン系重合体を得る工程である。
次いで、本発明の製造方法における第2工程について説明する。本発明の製造方法における第2工程は、上述した第1工程で得られた活性末端を有する共役ジエン系重合体の活性末端に、下記の式(1)で表される化合物を反応させることにより、変性共役ジエン系ゴムを得る工程である。
本発明のゴム組成物は、上述した本発明の製造方法により得られる変性共役ジエン系ゴムを含むゴム成分100重量部と、シリカ10〜200重量部とを含有してなるゴム組成物である。
本発明のゴム架橋物は、上述した本発明のゴム組成物を架橋してなるものである。本発明のゴム架橋物は、本発明のゴム組成物を用い、たとえば、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10〜200℃、好ましくは25〜120℃である。架橋温度は、通常、100〜200℃、好ましくは130〜190℃であり、架橋時間は、通常、1分〜24時間、好ましくは2分〜12時間、特に好ましくは3分〜6時間である。
変性共役ジエン系ゴムの分子量は、ゲルパーミエーションクロマトグラフィによりポリスチレン換算分子量として求めた。具体的な測定条件は、以下のとおりとした。
測定器:高速液体クロマトグラフ(東ソー社製、商品名「HLC−8220」)
カラム:東ソー社製、商品名「GMH−HR−H」を二本直列に連結した。
検出器:示差屈折計
溶離液:テトラヒドロフラン
カラム温度:40℃
低発熱性については、長さ50mm、幅12.7mm、厚さ2mmの試験片を、レオメトリックス社製ARESを用い、動的歪み2.5%、10Hzの条件で60℃におけるtanδを測定することにより評価した。このtanδの値については、比較例2の測定値を100とする指数で示した。この指数が小さいものほど、低発熱性に優れる。
ウエットグリップ性については、長さ50mm、幅12.7mm、厚さ2mmの試験片を、レオメトリックス社製ARESを用い、動的歪み0.5%、10Hzの条件で0℃におけるtanδの値を測定することにより評価した。このtanδの値については、比較例2の測定値を100とする指数で示した。この指数が大きいものほど、ウエットグリップ性に優れる。
窒素雰囲気下、オートクレーブに、シクロヘキサン800部、1,3−ブタジエン94.8部、スチレン25.2部、およびテトラメチルエチレンジアミン0.187部を仕込んだ後、n−ブチルリチウム0.045部を添加し、60℃で重合を開始した。60分間重合反応を継続し、重合転化率が95%から100%の範囲になったことを確認してから、3−(ベンジルメチルアミノ)プロピルトリメトキシシラン(下記の式(2)で表される化合物)0.224部(n−ブチルリチウムの使用量に対して、1.00倍モル)を添加し、30分間反応させた後、重合停止剤としてメタノール0.064部を添加して、共役ジエン系重合体を含有する溶液を得た。そして、得られた重合体成分100部に対して、老化防止剤として2,4−ビス[(オクチルチオ)メチル]−o−クレゾール(チバスペシャルティケミカルズ社製、商品名「イルガノックス1520」)0.15部を溶液に添加した後、スチームストリッピングにより、溶媒を除去し、60℃で24時間真空乾燥して、固形状の変性共役ジエン系ゴムを得た。得られた実施例1の変性共役ジエン系ゴムの重量平均分子量(Mw)は345,000、分子量分布(Mw/Mn)は1.20であった。
3−(ベンジルメチルアミノ)プロピルトリメトキシシランの添加量を、0.335部(n−ブチルリチウムの使用量に対して、1.50倍モル)に変更したこと以外は、実施例1と同様に操作して、固形状の変性共役ジエン系ゴムを得た。得られた実施例2の変性共役ジエン系ゴムの重量平均分子量(Mw)は300,000、分子量分布(Mw/Mn)は1.14であった。
3−(ベンジルメチルアミノ)プロピルトリメトキシシランに代えて、N−フェニル−2−ピロリドン0.027部(n−ブチルリチウムの使用量に対して、1.00倍モル)を添加したこと以外は、実施例1と同様に操作して、固形状の変性共役ジエン系ゴムを得た。得られた比較例1の変性共役ジエン系ゴムの重量平均分子量(Mw)は254,000、分子量分布(Mw/Mn)は1.09であった。
3−(ベンジルメチルアミノ)プロピルトリメトキシシランに代えて、3−(ジメチルアミノ)プロピルトリメトキシシラン(下記の式(3)で表される化合物)0.143部(n−ブチルリチウムの使用量に対して、1.00倍モル)を添加したこと以外は、実施例1と同様に操作して、固形状の変性共役ジエン系ゴムを得た。得られた比較例2の変性共役ジエン系ゴムの重量平均分子量(Mw)は380,000、分子量分布(Mw/Mn)は1.20であった。
3−(ベンジルメチルアミノ)プロピルトリメトキシシランに代えて、下記の式(4)で表されるポリオルガノシロキサン0.156部(n−ブチルリチウムの使用量に対して、0.28倍モル)を添加したこと以外は、実施例1と同様に操作して、固形状の変性共役ジエン系ゴムを得た。得られた比較例3の変性共役ジエン系ゴムの重量平均分子量(Mw)は555,000、分子量分布(Mw/Mn)は1.32であった。
容量250mlのブラベンダータイプミキサー中で、実施例1の変性共役ジエン系ゴム100部を30秒素練りし、次いでシリカ(ローディア社製、商品名「Zeosil1115MP」)50部、プロセスオイル(新日本石油社製、商品名「アロマックス T−DAE」)20部、およびシランカップリング剤:ビス(3−(トリエトキシシリル)プロピル)テトラスルフィド(デグッサ社製、商品名「Si69」)6.0部を添加して、110℃を開始温度として1.5分間混練後、シリカ(ローディア社製、商品名「Zeosil1115MP」)25部、酸化亜鉛3部、ステアリン酸2部および老化防止剤:N−フェニル−N’−(1,3−ジメチルブチル)−p−フェニレンジアミン(大内新興社製、商品名「ノクラック6C」)2部を添加し、更に2.5分間混練し、ミキサーから混練物を排出させた。混錬終了時の混練物の温度は150℃であった。混練物を、室温まで冷却した後、再度ブラベンダータイプミキサー中で、110℃を開始温度として2分間混練した後、ミキサーから混練物を排出させた。次いで、50℃のオープンロールで、得られた混練物に、硫黄1.40部、架橋促進剤:N−tert−ブチル−2−ベンゾチアゾリルスルフェンアミド(商品名「ノクセラーNS−P」、大内新興化学工業社製)1.2部、およびジフェニルグアニジン(商品名「ノクセラーD」、大内新興化学工業社製)1.2部を加えてこれらを混練した後、シート状のゴム組成物を取り出した。このゴム組成物を、160℃で20分間プレス架橋して、ゴム架橋物の試験片を作製し、この試験片について、低発熱性およびウエットグリップ性の評価を行なった。実施例2、比較例1、比較例2および比較例3の変性共役ジエン系ゴムについても、それぞれ、同様にして、ゴム架橋物の試験片を作製し、これらの試験片について、低発熱性およびウエットグリップ性の評価を行なった。表1にこれらの結果をまとめて示す。
Claims (9)
- 前記第2工程において、前記活性末端を有する共役ジエン系重合体が存在する不活性溶媒中に、前記活性末端を有する共役ジエン系重合体の活性末端1モルに対して、1〜3モルの割合で、前記式(1)で表される化合物を添加する請求項1に記載の変性共役ジエン系ゴムの製造方法。
- 前記活性末端を有する共役ジエン系重合体が、共役ジエン単量体単位50〜100重量%および芳香族ビニル単量体単位0〜50重量%を含む請求項1または2に記載の変性共役ジエン系ゴムの製造方法。
- 前記式(1)中、R1〜R3は、それぞれ独立して、メチル基またはエチル基であり、R4は、ベンジル基、フェネチル基、またはフェニルプロピル基であり、R5は、メチル基、エチル基またはプロピル基であり、nは3〜5の整数である請求項1〜3のいずれかに記載の変性共役ジエン系ゴムの製造方法。
- 請求項1〜4のいずれかに記載の変性共役ジエン系ゴムの製造方法により得られる変性共役ジエン系ゴム。
- 請求項5に記載の変性共役ジエン系ゴムを含むゴム成分100重量部と、シリカ10〜200重量部とを含有してなるゴム組成物。
- 架橋剤をさらに含有してなる請求項6に記載のゴム組成物。
- 請求項7に記載のゴム組成物を架橋してなるゴム架橋物。
- 請求項8に記載のゴム架橋物を含んでなるタイヤ。
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