JP2013129693A - Method for producing modified conjugated diene polymer and composition of modified conjugated diene polymer - Google Patents
Method for producing modified conjugated diene polymer and composition of modified conjugated diene polymer Download PDFInfo
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- JP2013129693A JP2013129693A JP2011278189A JP2011278189A JP2013129693A JP 2013129693 A JP2013129693 A JP 2013129693A JP 2011278189 A JP2011278189 A JP 2011278189A JP 2011278189 A JP2011278189 A JP 2011278189A JP 2013129693 A JP2013129693 A JP 2013129693A
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- Prior art keywords
- conjugated diene
- diene polymer
- modified conjugated
- group
- silica
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 120
- 150000001993 dienes Chemical class 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229920001971 elastomer Polymers 0.000 claims abstract description 54
- 239000005060 rubber Substances 0.000 claims abstract description 52
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000011256 inorganic filler Substances 0.000 claims abstract description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 15
- 238000006011 modification reaction Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000003607 modifier Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000003398 denaturant Substances 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 9
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- 238000009826 distribution Methods 0.000 description 8
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
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- 150000001339 alkali metal compounds Chemical class 0.000 description 7
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- 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 5
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- 239000012535 impurity Substances 0.000 description 5
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- 239000000047 product Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
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- 125000005369 trialkoxysilyl group Chemical group 0.000 description 4
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 3
- OBSCXZUWRCYEQX-UHFFFAOYSA-N 3-(2,2-dimethoxyazasilolidin-1-yl)propyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCN1CCC[Si]1(OC)OC OBSCXZUWRCYEQX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001361 allenes Chemical class 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000005677 ethinylene group Chemical class [*:2]C#C[*:1] 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- 235000014692 zinc oxide Nutrition 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- TZFZDYZBXPBFTL-UHFFFAOYSA-N 3-(2,2-diethoxyazasilolidin-1-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCC[Si]1(OCC)OCC TZFZDYZBXPBFTL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 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 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
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- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
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- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
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- JFFDVYGLAUESBW-UHFFFAOYSA-N 2,2-diethoxyethyl-[3-(2-ethoxy-2-ethylazasilolidin-1-yl)propyl]silane Chemical compound C(C)O[Si]1(N(CCC1)CCC[SiH2]CC(OCC)OCC)CC JFFDVYGLAUESBW-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LBNXIXUYCBHSCI-UHFFFAOYSA-N 3-(2,2-diethoxyazasilolidin-1-yl)propyl-(2,2-diethoxyethyl)silane Chemical compound C(C)O[Si]1(N(CCC1)CCC[SiH2]CC(OCC)OCC)OCC LBNXIXUYCBHSCI-UHFFFAOYSA-N 0.000 description 1
- WVKWROOWRSSQDU-UHFFFAOYSA-N 3-(2,2-dimethoxyazasilolidin-1-yl)propyl-(dimethoxymethyl)silane Chemical compound CO[Si]1(N(CCC1)CCC[SiH2]C(OC)OC)OC WVKWROOWRSSQDU-UHFFFAOYSA-N 0.000 description 1
- JZUWXDYZFYFWIX-UHFFFAOYSA-N 3-[3-(2-ethoxyethyl)imidazolidin-1-yl]propyl-trimethoxysilane Chemical compound CCOCCN1CCN(CCC[Si](OC)(OC)OC)C1 JZUWXDYZFYFWIX-UHFFFAOYSA-N 0.000 description 1
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 1
- BPRJCGGKXVEOPN-UHFFFAOYSA-N 4-(2,2-dimethoxyazasilinan-1-yl)butyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCCN1CCCC[Si]1(OC)OC BPRJCGGKXVEOPN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JPRQNNLGTDJVBA-UHFFFAOYSA-N 5-(2,2-dimethoxyazasilepan-1-yl)pentyl-trimethoxysilane Chemical compound CO[Si](OC)(OC)CCCCCN1CCCCC[Si]1(OC)OC JPRQNNLGTDJVBA-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- IIGVVBYWTLSFRA-UHFFFAOYSA-N tributoxy-[3-(1-methyl-2,4-dihydropyrimidin-3-yl)propyl]silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)CCCN1CC=CN(C)C1 IIGVVBYWTLSFRA-UHFFFAOYSA-N 0.000 description 1
- 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
- HPDURSIFGBKQQA-UHFFFAOYSA-N triethoxy-[3-(2-ethoxy-2-ethylazasilolidin-1-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCC[Si]1(CC)OCC HPDURSIFGBKQQA-UHFFFAOYSA-N 0.000 description 1
- LUHSQMWOOCBXIL-UHFFFAOYSA-N triethoxy-[3-(3-methyl-1,3-diazinan-1-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCCN(C)C1 LUHSQMWOOCBXIL-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
- LJSCMFMGPIFSDE-UHFFFAOYSA-N triethoxy-[3-(4-methylpiperazin-1-yl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN(C)CC1 LJSCMFMGPIFSDE-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本発明は、変性共役ジエン重合体の製造方法及び変性共役ジエン重合体を含む組成物に関する。 The present invention relates to a method for producing a modified conjugated diene polymer and a composition containing the modified conjugated diene polymer.
近年、二酸化炭素排出量の抑制等、環境に対する配慮が社会的要請となっており、自動車に対する低燃費化への要望が高まってきている。このような現状から、自動車用タイヤ、特に地面と接するタイヤトレッドの材料として、転がり抵抗が小さい材料の開発が求められている。
従来、タイヤトレッドの補強性充填剤としては、カーボンブラック、シリカ等が使用されている。補強性充填剤としてシリカを用いると、低ヒステリシスロス性及びウェットスキッド抵抗性の向上が図られるという利点を有している。
In recent years, environmental considerations, such as the suppression of carbon dioxide emissions, have become social demands, and the demand for lower fuel consumption for automobiles has increased. Under such circumstances, development of a material having low rolling resistance is demanded as a material for automobile tires, particularly tire treads that are in contact with the ground.
Conventionally, carbon black, silica, and the like have been used as reinforcing fillers for tire treads. When silica is used as the reinforcing filler, there is an advantage that low hysteresis loss and wet skid resistance can be improved.
一方、疎水性表面のカーボンブラックに対して、親水性表面のシリカは、共役ジエン系ゴムとの親和性が低く、カーボンブラックに比較して分散性が悪いという欠点を有していることから、分散性を改良させたり、シリカ-ゴム間の結合付与を行ったりするため、別途シランカップリング剤を含有させる必要がある。
このようなシリカに関する問題に鑑みて、運動性の高いゴム分子末端部に、シリカとの親和性や反応性を有する官能基を導入することによって、共役ジエン系ゴム材中におけるシリカの分散性を改良し、さらにはゴム分子末端部をシリカ粒子との結合で封じることによって、ヒステリシスロスを低減化する試みがなされている。
例えば、グリシジルアミノ基を有する変性剤を重合体末端に反応させて得られる変性ジエン系ゴム（例えば、特許文献１参照。）や、グリシドキシアルコキシシランを重合体末端に反応させて得られる変性ジエン系ゴム（例えば、特許文献２参照。）、さらにはアミノ基を含有するアルコキシシラン類を重合体末端に反応させて得られる変性ジエン系ゴム（例えば、特許文献３、４参照。）、及びこれらとシリカとの組成物についての提案がなされている。
また、変性剤の添加方法により分子量分布を制御する方法も開示されている（例えば、特許文献５参照）。
On the other hand, since silica with a hydrophilic surface has a low affinity with a conjugated diene rubber and has a disadvantage of poor dispersibility compared with carbon black, with respect to carbon black with a hydrophobic surface, In order to improve dispersibility or to provide a bond between silica and rubber, it is necessary to contain a silane coupling agent separately.
In view of such problems related to silica, the dispersibility of silica in a conjugated diene rubber material can be improved by introducing functional groups having affinity and reactivity with silica at the end of rubber molecules having high mobility. Attempts have been made to reduce the hysteresis loss by improving and further sealing the rubber molecule end with a bond with silica particles.
For example, a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer end (for example, see Patent Document 1) or a modification obtained by reacting a glycidoxyalkoxysilane with a polymer end. Diene rubbers (for example, see Patent Document 2), modified diene rubbers obtained by reacting alkoxysilanes containing amino groups at the polymer ends (for example, see Patent Documents 3 and 4), and There have been proposals for compositions of these with silica.
In addition, a method of controlling the molecular weight distribution by a modifying agent addition method is also disclosed (for example, see Patent Document 5).
しかしながら、近年においては、低燃費化の要求のさらなる高まりとともに、一層、ヒステリシスロスを低減化させたゴム組成物の開発が要求されるようになっている。
本発明の課題は、シリカ系無機充填剤と混合して加硫物としたときに、低ヒステリシスロス性とウェットスキッド抵抗性、引っ張り特性、耐摩耗性のバランスに優れたゴム組成物とすることができる、変性共役ジエン重合体の製造方法を提供することを目的とする。
However, in recent years, with the further increase in demand for fuel efficiency, development of a rubber composition having further reduced hysteresis loss has been demanded.
An object of the present invention is to provide a rubber composition having an excellent balance of low hysteresis loss, wet skid resistance, tensile properties, and abrasion resistance when mixed with a silica-based inorganic filler to obtain a vulcanized product. An object of the present invention is to provide a method for producing a modified conjugated diene polymer.
本発明者らは、前記従来技術の課題を解決するために鋭意研究を重ねた結果、従来の共役ジエン系ゴムの変性方法（共役ジエン系ゴムにシリカとの親和性や反応性を有する官能基を導入して変性する方法）では、共役ジエン系ゴムの変性率が十分でなく、その結果、シリカの分散性を十分に改良できていないことが分かった。
そして、共役ジエン系モノマー又は共役ジエン系モノマーと芳香族ビニルモノマーを重合させて活性末端を有する共役ジエン重合体（Ａ）を合成した後、（Ａ）をアルコキシシリル基を有する変性剤（Ｂ）を用いて変性させる場合には、両者を攪拌する際の撹拌動力を１〜５０ｋＷ／ｍ３とすると、変性率が格段に向上し、この方法によって得られる変性共役ジエン重合体（Ｃ）を、シリカ系無機充填剤と混合して、加硫物とすると、低ヒステリシスロス性、ウェットスキッド抵抗性、引っ張り特性、耐摩耗性のバランスに優れることを見出し、本発明を完成させるに至った。
本発明は以下の通りである。
活性末端を有する共役ジエン重合体（Ａ）を用意する工程、及び
前記共役ジエン重合体（Ａ）とアルコキシシリル基を有する変性剤（Ｂ）を混合撹拌し、両者を反応させる変性反応工程
を有する、変性共役ジエン重合体（Ｃ）の製造方法において、
前記変性反応工程における前記攪拌の撹拌動力が１〜５０ｋＷ／ｍ３である変性共役ジエン重合体（Ｃ）の製造方法。
As a result of intensive studies to solve the problems of the prior art, the present inventors have made a conventional modification method of conjugated diene rubber (functional group having affinity or reactivity with silica for conjugated diene rubber). It has been found that the modification rate of the conjugated diene rubber is not sufficient in the method of introducing and modifying the silica, and as a result, the dispersibility of the silica cannot be improved sufficiently.
Then, a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer are polymerized to synthesize a conjugated diene polymer (A) having an active terminal, and then (A) is a modifier having an alkoxysilyl group (B). In the case of modifying using the above, when the stirring power at the time of stirring both is 1 to 50 kW / m 3 , the modification rate is remarkably improved, and the modified conjugated diene polymer (C) obtained by this method, When mixed with a silica-based inorganic filler to obtain a vulcanized product, the present inventors have found that the balance between low hysteresis loss, wet skid resistance, tensile properties, and wear resistance is excellent, and the present invention has been completed.
The present invention is as follows.
A step of preparing a conjugated diene polymer (A) having an active end, and a modification reaction step of mixing and stirring the conjugated diene polymer (A) and a modifying agent (B) having an alkoxysilyl group, and reacting both. In the production method of the modified conjugated diene polymer (C),
The manufacturing method of the modified conjugated diene polymer (C) whose stirring power of the said stirring in the said modification reaction process is 1-50 kW / m < 3 >.
本発明の方法によれば、共役ジエン重合体（Ａ）がアルコキシシリル基を有する変性剤（Ｂ）により高い変性率で変性された、変性共役ジエン重合体（Ｃ）を得ることができる。なお、変性共役ジエン重合体（Ｃ）とは、変性反応によって少なくとも一部が変性された共役ジエン共重合体（Ａ）をいい、具体的には、共役ジエン共重合体（Ａ）とその変性体の混合物（ただし、変性率が１００％の場合は共役ジエン共重合体（Ａ）の変性体単独）である。
さらに、本発明の方法で製造された変性共役ジエン重合体（Ｃ）を、シリカ系無機充填剤と混合し、加硫物とすると、低ヒステリシスロス性、ウェットスキッド抵抗性、耐摩耗性、引っ張り特性のバランスに優れるゴム組成物が得られる。
According to the method of the present invention, it is possible to obtain a modified conjugated diene polymer (C) in which the conjugated diene polymer (A) is modified with a modifying agent (B) having an alkoxysilyl group at a high modification rate. The modified conjugated diene polymer (C) refers to a conjugated diene copolymer (A) that has been at least partially modified by a modification reaction. Specifically, the conjugated diene copolymer (A) and the modification thereof. Mixture (however, when the modification rate is 100%, the modified conjugated diene copolymer (A) alone).
Furthermore, when the modified conjugated diene polymer (C) produced by the method of the present invention is mixed with a silica-based inorganic filler to form a vulcanized product, low hysteresis loss, wet skid resistance, abrasion resistance, tensile A rubber composition having an excellent balance of properties can be obtained.
以下、本発明を実施するための形態（以下、「本実施形態」と言う。）について詳細に説明する。
なお、本発明は、以下の実施形態に制限されるものではなく、その要旨の範囲内で種々変形して実施することができる。
Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.
活性末端を有する共役ジエン重合体（Ａ）を用意する工程では、例えば、有機アルカリ金属化合物又は有機アルカリ土類金属化合物を重合開始剤として用い、共役ジエン化合物、又は共役ジエン化合物と芳香族ビニル化合物とを、重合又は共重合することで、活性末端を有する共役ジエン重合体（Ａ）を得ることができる。
ここで、変性共役ジエン重合体（Ｃ）を構成する共役ジエン重合体（Ａ）は、単一の共役ジエン化合物の重合体又は異なる種類の共役ジエン化合物の重合体すなわち共重合体、又は共役ジエン化合物と芳香族ビニル化合物の共重合体である。
In the step of preparing the conjugated diene polymer (A) having an active terminal, for example, an organic alkali metal compound or an organic alkaline earth metal compound is used as a polymerization initiator, and a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound are used. Can be polymerized or copolymerized to obtain a conjugated diene polymer (A) having an active end.
Here, the conjugated diene polymer (A) constituting the modified conjugated diene polymer (C) is a polymer of a single conjugated diene compound, a polymer or copolymer of different types of conjugated diene compounds, or a conjugated diene. It is a copolymer of a compound and an aromatic vinyl compound.
共役ジエン化合物は、重合可能な単量体であれば特に限定されず、例えば１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、３−メチル−１，３−ペンタジエン、１，３−ヘプタジエン、１，３−ヘキサジエン等が挙げられる。これらの中でも、工業的入手の容易さの観点から、１，３−ブタジエン、イソプレンが好ましい。これらは１種のみならず２種以上を併用してもよい。
芳香族ビニル化合物は、共役ジエン化合物と共重合可能な単量体であればよく、特に限定されず、例えばスチレン、ｍまたはｐ−メチルスチレン、α−メチルスチレン、ビニルエチルベンゼン、ビニルキシレン、ビニルナフタレン、ジフェニルエチレン、ジビニルベンゼン等が挙げられる。これらの中でも、工業的入手の容易さの観点から、スチレンが好ましい。これらは１種のみならず２種以上を併用してもよい。
The conjugated diene compound is not particularly limited as long as it is a polymerizable monomer. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl- 1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.
The aromatic vinyl compound is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, m or p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene. , Diphenylethylene, divinylbenzene and the like. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.
共役ジエン化合物中に、アレン類、アセチレン類等が不純物として含有されていると、後述する変性反応を阻害するおそれがある。そのため、これらの不純物の含有量濃度（質量）の合計は、２００ｐｐｍ以下であることが好ましく、１００ｐｐｍ以下であることがより好ましく、５０ｐｐｍ以下であることが更に好ましい。
アレン類としては、例えばプロパジエン、１，２−ブタジエン等が挙げられる。アセチレン類としては、例えばエチルアセチレン、ビニルアセチレン等が挙げられる。
If the conjugated diene compound contains allenes, acetylenes or the like as impurities, there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.
Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.
共役ジエン重合体（Ａ）が共重合体である場合、ランダム共重合体であってもブロック共重合体であってもよい。
ランダム共重合体としては、例えばブタジエン−イソプレンランダム共重合体、ブタジエン−スチレンランダム共重合体、イソプレン−スチレンランダム共重合体、ブタジエン−イソプレン−スチレンランダム共重合体等が挙げられる。共重合体鎖中の各単量体の組成分布は特に限定されないが、例えば統計的ランダムな組成に近い完全ランダム共重合体、組成分布に勾配があるテーパー（勾配）ランダム共重合体等が挙げられる。共役ジエンの結合様式、すなわち１，４−結合や１，２−結合等の組成は、分子鎖によって均一であってもよいし、異なっていてもよい。
When the conjugated diene polymer (A) is a copolymer, it may be a random copolymer or a block copolymer.
Examples of the random copolymer include a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer. The composition distribution of each monomer in the copolymer chain is not particularly limited, and examples thereof include a completely random copolymer close to a statistical random composition, and a tapered (gradient) random copolymer having a gradient in composition distribution. It is done. The bonding mode of the conjugated diene, that is, the composition such as 1,4-bond or 1,2-bond may be uniform or different depending on the molecular chain.
ブロック共重合体としては、例えばブロックが２個からなる２型ブロック共重合体、３個からなる３型ブロック共重合体、４個からなる４型ブロック共重合体等が挙げられる。ここでスチレン等の芳香族ビニル化合物からなるブロックをＳで表し、ブタジエンやイソプレン等の共役ジエン化合物からなるブロック及び／又は芳香族ビニル化合物と共役ジエン化合物との共重合体からなるブロックをＢで表すと、Ｓ−Ｂ２型ブロック共重合体、Ｓ−Ｂ−Ｓ３型ブロック共重合体、Ｓ−Ｂ−Ｓ−Ｂ４型ブロック共重合体等で表される。
上式において、各ブロックの境界は必ずしも明瞭に区別される必要はない。例えばブロックＢが芳香族ビニル化合物と共役ジエン化合物との共重合体の場合、ブロックＢ中の芳香族ビニル化合物は均一に分布していても、又はテーパー状に分布していてもよい。また、ブロックＢに、芳香族ビニル化合物が均一に分布している部分及び／又はテーパー状に分布している部分がそれぞれ複数個共存していてもよい。さらには、ブロックＢに、芳香族ビニル化合物含有量が異なるセグメントが複数個共存していてもよい。共重合体中にブロックＳ、ブロックＢがそれぞれ複数存在する場合、それらの分子量や組成等の構造は、同一でもよいし、異なっていてもよい。
Examples of the block copolymer include a 2 type block copolymer comprising 2 blocks, a 3 type block copolymer comprising 3 blocks, and a 4 type block copolymer comprising 4 blocks. Here, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. When expressed, it is represented by an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, or the like.
In the above equation, the boundaries of each block need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.
重合開始剤として用いる有機アルカリ金属化合物としては、特に限定されないが、有機リチウム化合物が好ましい。有機リチウム化合物としては、低分子化合物や可溶化したオリゴマーの有機リチウム化合物が挙げられ、また、有機基とリチウムの結合様式においては、炭素−リチウム結合からなる化合物、窒素−リチウム結合からなる化合物、錫−リチウム結合からなる化合物等が挙げられる。
炭素−リチウム結合を有する有機リチウム化合物としては、例えばｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、ｎ−ヘキシルリチウム、ベンジルリチウム、フェニルリチウム、スチルベンリチウム等が挙げられる。
窒素−リチウム結合からなる有機リチウム化合物としては、例えばリチウムジメチルアミド、リチウムジエチルアミド、リチウムジプロピルアミド、リチウムジ−ｎ−ヘキシルアミド、リチウムジイソプロピルアミド、リチウムヘキサメチレンイミド、リチウムピロリジド、リチウムピペリジド、リチウムヘプタメチレンイミド、リチウムモルホリド等が挙げられる。
The organic alkali metal compound used as the polymerization initiator is not particularly limited, but an organic lithium compound is preferable. Examples of the organolithium compound include low molecular weight compounds and solubilized oligomeric organolithium compounds, and in the bonding mode between an organic group and lithium, a compound comprising a carbon-lithium bond, a compound comprising a nitrogen-lithium bond, Examples thereof include compounds composed of a tin-lithium bond.
Examples of the organic lithium compound having a carbon-lithium bond include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene lithium.
Examples of the organic lithium compound composed of a nitrogen-lithium bond include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, Examples thereof include lithium heptamethylene imide and lithium morpholide.
有機リチウム化合物としては、上記のモノ有機リチウム化合物だけでなく、多官能有機リチウム化合物を使用して、又は、モノ有機リチウム化合物と併用して重合させることもできる。
多官能有機リチウム化合物としては、例えば１，４−ジリチオブタン、ｓｅｃ−ブチルリチウムとジイソプロペニルベンゼンの反応物、１，３，５−トリリチオベンゼン、ｎ−ブチルリチウムと１，３−ブタジエン及びジビニルベンゼンの反応物、ｎ−ブチルリチウムとポリアセチレン化合物の反応物等が挙げられる。さらに、米国特許第５，７０８，０９２号明細書、英国特許第２，２４１，２３９号明細書、米国特許第５，５２７，７５３号明細書等に開示されている有機アルカリ金属化合物も使用することができる。
As the organolithium compound, not only the monoorganolithium compound described above but also a polyfunctional organolithium compound can be used, or polymerization can be performed in combination with the monoorganolithium compound.
Examples of the polyfunctional organolithium compound include 1,4-dilithiobutane, a reaction product of sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, n-butyllithium, 1,3-butadiene and divinyl. Examples include a reaction product of benzene, a reaction product of n-butyllithium and a polyacetylene compound. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.
有機リチウム化合物としては、工業的入手の容易さ及び重合反応のコントロールの容易さの観点から、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウムが好ましい。
有機リチウム化合物は１種のみならず２種以上の混合物として用いてもよい。
As the organic lithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction.
The organic lithium compound may be used as a mixture of not only one type but also two or more types.
他の有機アルカリ金属化合物としては、例えば有機ナトリウム化合物、有機カリウム化合物、有機ルビジウム化合物、有機セシウム化合物等が挙げられる。具体的には、ナトリウムナフタレン、カリウムナフタレン等が挙げられる。その他にも、リチウム、ナトリウム及びカリウム等のアルコキサイド、スルフォネート、カーボネート、アミド等が挙げられる。
また、上述した有機アルカリ金属化合物は、有機アルカリ土類金属化合物やその他の有機金属化合物と併用してもよい。
Examples of other organic alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given.
The organic alkali metal compound described above may be used in combination with an organic alkaline earth metal compound or other organic metal compound.
重合開始剤として用いる有機アルカリ土類金属化合物としては、有機マグネシウム化合物、有機カルシウム化合物、有機ストロンチウム化合物等が挙げられる。また、アルカリ土類金属のアルコキサイド、スルフォネート、カーボネート、アミド等の化合物を用いてもよい。これらの有機アルカリ土類金属化合物は、アルカリ金属化合物や、その他有機金属化合物と併用してもよい。 Examples of the organic alkaline earth metal compound used as the polymerization initiator include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with alkali metal compounds or other organic metal compounds.
活性末端を有する共役ジエン重合体（Ａ）は、上述した有機アルカリ金属化合物及び／又は有機アルカリ土類金属化合物を重合開始剤とし、共役ジエン化合物、又は、共役ジエン化合物と芳香族ビニル化合物をアニオン重合（共重合）させることにより得られる。特に、共役ジエン重合体（Ａ）は、リビングアニオン重合による成長反応によって得られる活性末端を有する重合体であることがより好ましい。これにより、高変性率の変性共役ジエン重合体を得ることができる。 The conjugated diene polymer (A) having an active end is obtained by using the above-mentioned organic alkali metal compound and / or organic alkaline earth metal compound as a polymerization initiator, and converting the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound into an anion. It is obtained by polymerization (copolymerization). In particular, the conjugated diene polymer (A) is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.
重合プロセスとしては連続式、バッチ式、セミバッチ式の何れのプロセスでも良いが、タイヤ原料として用いた時の耐摩耗性が良いことから連続式が好ましい。連続式においては、１個又は２個以上の連結された反応器を用いることができるが、２個以上用いると分子量分布を狭くすることもできるなど、分子量分布の制御の観点からも好ましい。反応器は、例えば撹拌機付きの槽型、管型等を用いることができる。 The polymerization process may be a continuous process, a batch process, or a semi-batch process, but a continuous process is preferred because of good wear resistance when used as a tire raw material. In the continuous system, one or two or more connected reactors can be used, but the use of two or more reactors is preferable from the viewpoint of controlling the molecular weight distribution, for example, the molecular weight distribution can be narrowed. As the reactor, for example, a tank type with a stirrer, a pipe type, or the like can be used.
共役ジエン化合物又は共役ジエン化合物と芳香族ビニル化合物の重合反応は、溶媒中で行うことが好ましい。溶媒としては、例えば飽和炭化水素、芳香族炭化水素等の炭化水素系溶媒が挙げられる。具体的には、ブタン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン等の脂環族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素及びそれらの混合物からなる炭化水素等が挙げられる。 The polymerization reaction of the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound is preferably performed in a solvent. Examples of the solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples thereof include hydrocarbons composed of a mixture thereof.
重合反応に供する前に、不純物であるアレン類やアセチレン類を有機金属化合物で処理することは、高濃度の活性末端を有する重合体が得られる傾向にあり、更には高い変性率が達成される傾向にあるため好ましい。
共役ジエン化合物の重合反応においては、極性化合物を添加してもよい。極性化合物は、芳香族ビニル化合物を共役ジエン化合物とランダムに共重合させるために用いることができ、共役ジエン部のミクロ構造を制御するためのビニル化剤としても用いることができる。また、重合速度の改善等にも効果がある。
極性化合物としては、特に限定されず、例えばテトラヒドロフラン、ジエチルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジメトキシベンゼン、２，２−ビス（２−オキソラニル）プロパン等のエーテル類；テトラメチルエチレンジアミン、ジピペリジノエタン、トリメチルアミン、トリエチルアミン、ピリジン、キヌクリジン等の第３級アミン化合物；カリウム−ｔ−アミラート、カリウム−ｔ−ブチラート、ナトリウム−ｔ−ブチラート、ナトリウムアミラート等のアルカリ金属アルコキシド化合物；トリフェニルホスフィン等のホスフィン化合物等を用いることができる。これらの極性化合物は、それぞれ単独で用いてもよく２種以上を組み合わせて用いてもよい。
Treatment of allenes and acetylenes, which are impurities, with an organometallic compound before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and a high modification rate is achieved. It is preferable because of its tendency.
In the polymerization reaction of the conjugated diene compound, a polar compound may be added. The polar compound can be used for randomly copolymerizing an aromatic vinyl compound with a conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. It is also effective in improving the polymerization rate.
The polar compound is not particularly limited, and examples thereof include tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl) propane, and the like. Ethers; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t-butylate, sodium amylate, etc. Alkali metal alkoxide compounds of the above; phosphine compounds such as triphenylphosphine can be used. These polar compounds may be used alone or in combination of two or more.
極性化合物の使用量は、特に限定されず、目的等に応じて選択することができる。通常、重合開始剤１モルに対して０．０１〜１００モルであることが好ましい。このような極性化合物（ビニル化剤）は重合体共役ジエン部分のミクロ構造の調節剤として、所望のビニル結合量に応じて、適量用いることができる。
多くの極性化合物は、同時に共役ジエン化合物と芳香族ビニル化合物との共重合において有効なランダム化効果を有し、芳香族ビニル化合物の分布の調整やスチレンブロック量の調整剤として用いることができる。共役ジエン化合物と芳香族ビニル化合物とをランダム化する方法としては、例えば特開昭５９−１４０２１１号公報に記載されているような、共重合の途中に１，３−ブタジエンの一部を断続的に添加する方法を用いてもよい。
The usage-amount of a polar compound is not specifically limited, It can select according to the objective etc. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators. An appropriate amount of such a polar compound (vinylating agent) can be used as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount.
Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently produced during the copolymerization. You may use the method of adding to.
重合温度は重合が進行する温度であれば、特に限定されないが、生産性の観点から、０℃以上であることが好ましく、重合終了後の活性末端に対する変性剤の反応量を充分に確保する観点から、１２０℃以下であることが好ましい。また、共役ジエン系重合体のコールドフローを防止する観点から、分岐をコントロールするためのジビニルベンゼン等の多官能芳香族ビニル化合物を用いてもよい。 The polymerization temperature is not particularly limited as long as the polymerization proceeds, but from the viewpoint of productivity, it is preferably 0 ° C. or higher, and the viewpoint of sufficiently securing the reaction amount of the modifier with respect to the active terminal after the polymerization is completed. Therefore, it is preferably 120 ° C. or lower. Further, from the viewpoint of preventing cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene for controlling branching may be used.
例えば以上のような方法で、活性末端を有する共役ジエン重合体（Ａ）を用意した後、その活性末端に、アルコキシシリル基を有する変性剤（Ｂ）を反応させることで、変性共役ジエン重合体（Ｃ）を得ることができる。 For example, after preparing a conjugated diene polymer (A) having an active end by the method as described above, a modified conjugated diene polymer is reacted with a modifier (B) having an alkoxysilyl group at the active end. (C) can be obtained.
アルコキシシリル基を有する変性剤（Ｂ）としては、例えば、下記一般式（１）で表される化合物が挙げられる。 Examples of the modifier (B) having an alkoxysilyl group include a compound represented by the following general formula (1).
（式中、ＸはＣｌ，Ｂｒ，Ｉのいずれか１つから選ばれ、Ｒ１，Ｒ２はアルキル基、アリール基、ビニル基のいずれか１つ、ｍは１〜４の整数、ｎは１〜３の整数、ｍ＋ｎは２〜４である）
(In the formula, X is selected from any one of Cl, Br, and I, R1 and R2 are any one of an alkyl group, an aryl group, and a vinyl group, m is an integer of 1 to 4, and n is 1 to 4) An integer of 3, m + n is 2-4)
なお、Ｒ１、Ｒ２は、置換されていてもよい。
具体例としては、ジメトキシジメチルシラン、キシジメチルシラン、ジエトキシジエチルシラン、トリフェノキシビニルシラン、トリメトキシビニルシラン、トリエトキシビニルシラン、トリ（２−メチルブトキシ）エチルシラン、トリ（２−メチルブトキシ）ビニルシラン、トリフェノキシフェニルシラン、テトラフェノキシシラン、テトラエトキシシラン、テトラメトキシシラン、テトラキス（２−エチルヘキシルオキシ）シラン、フェノキシジビニルクロロシラン、メトキシジエチルクロロシラン、ジフェノキシメチルクロロシラン、ジフェノキシフェニルヨードシラン、ジエトキシメチルクロロシラン、ジメトキシエチルクロロシラン、トリエトキシクロロシラン、トリフェノキシクロロシラン、トリス（２−エチルヘキシルオキシ）クロロシラン、フェノキシメチルジクロロシラン、メトキシエチルジクロロシラン、エトキシメチルジクロロシラン、フェノキシフェニルジヨードシラン、フェノキシジクロロシラン、ジメトキシジクロロシラン、ビス（２−メチルブトキシ）ジブロモシラン等が挙げられる。
R 1 and R 2 may be substituted.
Specific examples include dimethoxydimethylsilane, xidimethylsilane, diethoxydiethylsilane, triphenoxyvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tri (2-methylbutoxy) ethylsilane, tri (2-methylbutoxy) vinylsilane, triphenoxy. Phenylsilane, tetraphenoxysilane, tetraethoxysilane, tetramethoxysilane, tetrakis (2-ethylhexyloxy) silane, phenoxydivinylchlorosilane, methoxydiethylchlorosilane, diphenoxymethylchlorosilane, diphenoxyphenyliodosilane, diethoxymethylchlorosilane, dimethoxyethyl Chlorosilane, triethoxychlorosilane, triphenoxychlorosilane, tris (2-ethylhexyloxy) Chlorosilanes, phenoxymethyl dichlorosilane, methoxyethyl dichlorosilane, ethoxymethyl dichlorosilane, phenoxyphenyl diiodo silane, phenoxy dichlorosilane, dimethoxy dichlorosilane, bis (2-methylbutoxy) dibromo silane, and the like.
更に、アルコキシシリル基を有する変性剤（Ｂ）としては、分子内にＮ原子と複数個のアルコキシシリル基を有する一般式（２）又は（３）で表される化合物を用いることが好ましい。 Furthermore, as the modifier (B) having an alkoxysilyl group, a compound represented by the general formula (2) or (3) having an N atom and a plurality of alkoxysilyl groups in the molecule is preferably used.
（式（２）中、Ｒ1〜Ｒ4は、各々独立して、炭素数１〜２０のアルキル基又はアリール基を表し、Ｒ5は炭素数１〜１０のアルキレン基を表し、Ｒ6は炭素数１〜２０のアルキレン基を表し、ｍは１又は２の整数であり、ｎは２又は３の整数である。）
(In Formula (2), R < 1 > -R < 4 > respectively independently represents a C1-C20 alkyl group or an aryl group, R < 5 > represents a C1-C10 alkylene group, R < 6 > is Represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, and n is an integer of 2 or 3.)
（式（３）中、Ｒ１、Ｒ２は、各々独立して炭素数１〜２０のアルキル基、又はアリール基であり、Ｒ３は炭素数１〜２０のアルキレン基であり、Ｒ４、Ｒ５は炭素数１〜６の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ６は炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｎは、２又は３の整数である。）
(In the formula (3), R 1, R 2 are each independently an alkyl group having 1 to 20 carbon atoms, or an aryl group, R 3 is an alkylene group having 1 to 20 carbon atoms, R 4, R 5 is a hydrocarbon group having 1 to 6 carbon atoms and has a ring structure of 5 or more members with two adjacent Ns, and R 6 has no hydrocarbon group having 1 to 20 carbon atoms and active hydrogen (It is a C1-C20 hydrocarbon group substituted by a hetero atom, or a 3 organic substituted silyl group, and n is an integer of 2 or 3.)
なお、Ｒ１〜Ｒ６は、置換されていてもよい。
一般式（２）で表される変性剤としては、例えば２，２−ジメトキシ−１−（３−トリメトキシシリルプロピル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（３−トリエトキシシリルプロピル）−１−アザ−２−シラシクロペンタン、２，２−ジメトキシ−１−（４−トリメトキシシリルブチル）−１−アザ−２−シラシクロヘキサン、２，２−ジメトキシ−１−（５−トリメトキシシリルペンチル）−１−アザ−２−シラシクロヘプタン、２，２−ジメトキシ−１−（３−ジメトキシメチルシリルプロピル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（３−ジエトキシエチルシリルプロピル）−１−アザ−２−シラシクロペンタン、２−メトキシ，２−メチル−１−（３−トリメトキシシリルプロピル）−１−アザ−２−シラシクロペンタン、２−エトキシ，２−エチル−１−（３−トリエトキシシリルプロピル）−１−アザ−２−シラシクロペンタン、２−メトキシ，２−メチル−１−（３−ジメトキシメチルシリルプロピル）−１−アザ−２−シラシクロペンタン、２−エトキシ，２−エチル−１−（３−ジエトキシエチルシリルプロピル）−１−アザ−２−シラシクロペンタン等が挙げられる。これらの中でも、変性剤の官能基とシリカ等の無機充填剤との反応性及び相互作用性の観点や、引っ張り特性の観点から、ｍが２、ｎが３であるものが好ましい。具体的には、２，２−ジメトキシ−１−（３−トリメトキシシリルプロピル）−１−アザ−２−シラシクロペンタン、２，２−ジエトキシ−１−（３−トリエトキシシリルプロピル）−１−アザ−２−シラシクロペンタンが好ましい。
R 1 to R 6 may be substituted.
Examples of the modifying agent represented by the general formula (2) include 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-Triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy -1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2 , 2-Diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilyl) Propyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl- 1- (3-Dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane Etc. Among these, m is 2 and n is 3 from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and tensile properties. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is preferred.
一般式（３）で示される変性剤としては、例えば１−[３−（トリアルコキシシリル）−プロピル]−４−アルキルピペラジン、１−[３−（アルキルジアルコキシシリル）−プロピル]−４−アルキルピペラジン、１−[３−（トリアルコキシシリル）−プロピル]−３−アルキルイミダゾリジン、１−[３−（アルキルジアルコキシシリル）−プロピル]−３−アルキルイミダゾリジン、１−[３−（トリアルコキシシリル）−プロピル]−３−アルキルヘキサヒドロピリミジン、１−[３−（アルキルジアルコキシシリル）−プロピル]−３−アルキルヘキサヒドロピリミジン、３−[３−（トリアルコキシシリル）−プロピル]−１−アルキル−１，２，３，４−テトラヒドロピリミジン、３−[３−（アルキルジアルコキシシリル）−プロピル]−１−アルキル−１，２，３，４−テトラヒドロピリミジン等であり、具体的には以下のような化合物が挙げられる。
即ち、１−[３−（トリエトキシシリル）−プロピル]−４−メチルピペラジン、１−[３−（ジエトキシエチルシリル）−プロピル]−４−メチルピペラジン、１−[３−（トリメトキシシリル）−プロピル]−３−メチルイミダゾリジン、１−[３−（ジエトキシエチルシリル）−プロピル]−３−エチルイミダゾリジン、１−[３−（トリエトキシシリル）−プロピル]−３−メチルヘキサヒドロピリミジン、１−[３−（ジメトキシメチルシリル）−プロピル]−３−メチルヘキサヒドロピリミジン、３−[３−（トリブトキシシリル）−プロピル]−１−メチル−１，２，３，４−テトラヒドロピリミジン、３−[３−（ジメトキシメチルシリル）−プロピル]−１−エチル−１，２，３，４−テトラヒドロピリミジン、１−（２−エトキシエチル）−３−[３−（トリメトキシシリル）−プロピル]−イミダゾリジン、（２−｛３−[３−（トリメトキシシリル）−プロピル]−テトラヒドロピリミジン−１−イル｝−エチル）ジメチルアミン等が挙げられる。好ましい化合物としては、１−[３−（トリエトキシシリル）−プロピル]−４−メチルピペラジンである。
Examples of the modifying agent represented by the general formula (3) include 1- [3- (trialkoxysilyl) -propyl] -4-alkylpiperazine, 1- [3- (alkyldialkoxysilyl) -propyl] -4- Alkylpiperazine, 1- [3- (trialkoxysilyl) -propyl] -3-alkylimidazolidine, 1- [3- (alkyldialkoxysilyl) -propyl] -3-alkylimidazolidine, 1- [3- ( Trialkoxysilyl) -propyl] -3-alkylhexahydropyrimidine, 1- [3- (alkyldialkoxysilyl) -propyl] -3-alkylhexahydropyrimidine, 3- [3- (trialkoxysilyl) -propyl] -1-alkyl-1,2,3,4-tetrahydropyrimidine, 3- [3- (alkyldialkoxysilyl) -propyl] -1-a Examples include rualkyl-1,2,3,4-tetrahydropyrimidine, and specific examples thereof include the following compounds.
That is, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) -propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) ) -Propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) -propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilyl) -propyl] -3-methylhexa Hydropyrimidine, 1- [3- (dimethoxymethylsilyl) -propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl) -propyl] -1-methyl-1,2,3,4 Tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) -propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3 -[3- (trimethoxysilyl) -propyl] -imidazolidine, (2- {3- [3- (trimethoxysilyl) -propyl] -tetrahydropyrimidin-1-yl} -ethyl) dimethylamine, etc. . A preferred compound is 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine.
共役ジエン重合体（Ａ）と変性剤（Ｂ）を撹拌、反応させる際の撹拌動力は、変性率の観点から１〜５０ｋＷ／ｍ３の範囲とする。好ましくは５〜４０ｋＷ／ｍ３、特に好ましくは１０〜３０ｋＷ／ｍ３、とりわけ好ましくは１０〜２５ｋＷ／ｍ３である。
ここで変性率とは共役ジエン重合体（Ａ）のうち、変性剤（Ｂ）と反応したものの割合のことであり、下記の方法で求められる値である。変性率は６０％以上であることが好ましく、より好ましくは７０％以上である。
ポリスチレン系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料のピーク面積をＰ１、標準ポリスチレンのピーク面積をＰ２、シリカ系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料の面積をＰ３、標準ポリスチレンのピーク面積をＰ４として、下記式より変性率（％）を求めた。
変性率（％）＝［１−（Ｐ２×Ｐ３）／（Ｐ１×Ｐ４）］×１００
（ただし、Ｐ１＋Ｐ２＝Ｐ３＋Ｐ４＝１００）
変性率の測定には、変性された共役ジエン重合体との親和性が高く吸着能が高いシリカ等の極性成分をカラム充填剤に用いたカラムクロマトグラフィーが有用である。これにより変性された重合体と非変性重合体の充填剤への吸着能の差を利用して、両者を分離、定量することができる。
The stirring power for stirring and reacting the conjugated diene polymer (A) and the modifier (B) is in the range of 1 to 50 kW / m 3 from the viewpoint of the modification rate. Preferably 5~40kW / m 3, particularly preferably 10~30kW / m 3, especially preferably 10~25kW / m 3.
Here, the modification rate is the proportion of the conjugated diene polymer (A) that has reacted with the modifier (B), and is a value determined by the following method. The modification rate is preferably 60% or more, more preferably 70% or more.
Sample with 100 as the total peak area of the chromatogram using the polystyrene column, P1 as the peak area of the sample, P2 as the peak area of the standard polystyrene, and 100 as the entire peak area of the chromatogram using the silica column The modification ratio (%) was obtained from the following formula, with the area of P3 being P3 and the peak area of standard polystyrene being P4.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)
For the measurement of the modification rate, column chromatography using a polar component such as silica, which has high affinity with the modified conjugated diene polymer and high adsorption ability, as a column filler is useful. Thus, both can be separated and quantified by utilizing the difference in the adsorption ability of the modified polymer and the unmodified polymer to the filler.
変性反応は連続式、バッチ式の何れの方法でもよいが、バッチごとの反応器の洗浄が不要であることや変性反応の均一性の観点から連続式が好ましい。連続式とは反応器に共役ジエン重合体（Ａ）と変性剤（Ｂ）を連続的に供給し、反応生成物を連続的に排出する反応プロセスであり、バッチ式とは予め共役ジエン重合体（Ａ）の溶液を反応器に仕込み、そこに所定量の変性剤（Ｂ）を添加して、混合、反応させ、反応が終了した段階で反応器内の反応生成物を全て排出するプロセスである。 The denaturation reaction may be either a continuous type or a batch type method, but the continuous type is preferred from the viewpoint of eliminating the need for washing the reactor for each batch and the uniformity of the denaturing reaction. The continuous type is a reaction process in which the conjugated diene polymer (A) and the modifier (B) are continuously supplied to the reactor and the reaction product is continuously discharged. The batch type is a conjugated diene polymer in advance. A process in which the solution of (A) is charged into a reactor, a predetermined amount of the modifier (B) is added thereto, mixed and reacted, and all reaction products in the reactor are discharged when the reaction is completed. is there.
変性反応器の形状は特に限定されないが、滞留時間制御などの反応操作性の自由度の高さから槽型が好ましい。
変性反応器の撹拌に用いる撹拌翼は特に限定されないが、具体的にはパドル翼、後退翼、アンカー翼、タービン翼等を使用するできることができ、異なる種類の撹拌翼を１本の撹拌軸の上段、下段に組み合わせて使用することもできる。
撹拌翼の翼枚数は特に制限はないが、撹拌効率の観点から２〜６枚が好ましい。
変性反応器には反応液の混合性をより高めるために邪魔板を取り付けることもできる。
The shape of the denaturing reactor is not particularly limited, but a tank type is preferable because of high degree of freedom of reaction operability such as residence time control.
The stirring blade used for stirring in the denaturation reactor is not particularly limited, but specifically, paddle blades, swept blades, anchor blades, turbine blades, etc. can be used, and different types of stirring blades can be used for one stirring shaft. A combination of the upper and lower stages can also be used.
The number of stirring blades is not particularly limited, but is preferably 2 to 6 from the viewpoint of stirring efficiency.
A baffle plate can be attached to the denaturing reactor in order to further improve the mixing of the reaction solution.
変性反応の温度は好ましくは５０〜１００℃、より好ましくは６５〜９５℃である。温度が低いと共役ジエン重合体（Ａ）の活性末端の安定性が良くなり失活を抑制できるという利点があり、一方、温度が高いとポリマー溶液の粘度が減少して撹拌効率が増す上に、反応速度も高くなるという利点がある。 The temperature of the modification reaction is preferably 50 to 100 ° C, more preferably 65 to 95 ° C. When the temperature is low, there is an advantage that the stability of the active terminal of the conjugated diene polymer (A) is improved and deactivation can be suppressed. On the other hand, when the temperature is high, the viscosity of the polymer solution is reduced and the stirring efficiency is increased. , There is an advantage that the reaction rate is also increased.
本発明においては、活性末端を有する共役ジエン重合体（A）を用意した後、これと前記変性剤（Ｂ）を反応させる前または後に、前記共役ジエン重合体（Ａ）の活性末端と多官能性変性剤を反応させることが好ましい。これにより、共役ジエン重合体（Ａ）の少なくとも一部を多官能性変性剤でカップリングさせて、前記変性剤（Ｂ）を反応させた変性基を有する共役ジエン重合体と多官能性変性剤でカップリングされた共役ジエン系重合体の組成物とすることができる。多官能性変性剤を使用することにより、コールドフロー性及び加工性が改良される。多官能性変性剤としては好適にはエポキシ基、カルボニル基、カルボン酸エステル基、カルボン酸アミド基、酸無水物基、リン酸エステル基、亜リン酸エステル基、エピチオ基、チオカルボニル基、チオカルボン酸エステル基、ジチオカルボン酸エステル基、チオカルボン酸アミド基、イミノ基、エチレンイミノ基、ハロゲン基、アルコキシシリル基、イソシアネート基、チオイソシアネート基、共役ジエン基、アリールビニル基から選択される１種以上の官能基を有する化合物が用いられる。 In the present invention, after preparing a conjugated diene polymer (A) having an active end, and before or after reacting it with the modifier (B), the active end of the conjugated diene polymer (A) and the polyfunctional It is preferable to react a sex modifier. Thereby, at least a part of the conjugated diene polymer (A) is coupled with a polyfunctional modifier, and the conjugated diene polymer having a modifying group obtained by reacting the modifier (B) with the multifunctional modifier. It can be set as the composition of the conjugated diene type polymer coupled by this. By using a multifunctional modifier, cold flow properties and processability are improved. The polyfunctional modifier is preferably an epoxy group, carbonyl group, carboxylic acid ester group, carboxylic acid amide group, acid anhydride group, phosphoric acid ester group, phosphite group, epithio group, thiocarbonyl group, thiocarboxylic acid One or more selected from an acid ester group, a dithiocarboxylic acid ester group, a thiocarboxylic acid amide group, an imino group, an ethyleneimino group, a halogen group, an alkoxysilyl group, an isocyanate group, a thioisocyanate group, a conjugated diene group, and an arylvinyl group A compound having a functional group of
多官能性変性剤としては、シリカとの親和性の大きい官能基を有するものが好ましく、またカップリングによる分子量の向上効果の大きいものが好ましい。具体的には、４〜６官能のポリエポキシ化合物あるいは合計で４〜６官能のエポキシ基とアルコキシシリル基の両方を有する化合物である。特に好ましくは、分子中にアミノ基を含むグリシジル化合物、更には１分子中にジグリシジルアミノ基を２個または３個有する化合物である。例えば、テトラグリシジルメタキシレンジアミン、テトラグリシジルアミノジフェニルメタン、テトラグリシジル−ｐ−フェニレンジアミン、ジグリシジルアミノメチルシクロヘキサン、テトラグリシジル−１，３−ビスアミノメチルシクロヘキサンなどである。これらの多官能性変性剤は単独又は，２種以上を併用することもできる。 As the polyfunctional modifier, those having a functional group having high affinity with silica are preferable, and those having a large effect of improving the molecular weight by coupling are preferable. Specifically, it is a 4-6 functional polyepoxy compound or a compound having both a 4-6 functional epoxy group and an alkoxysilyl group in total. Particularly preferred are glycidyl compounds containing an amino group in the molecule, and further compounds having two or three diglycidylamino groups in one molecule. For example, tetraglycidyl metaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane and the like. These polyfunctional modifiers can be used alone or in combination of two or more.
変性反応を行った後、反応溶液に、必要に応じて、失活剤、中和剤等を添加してもよい。失活剤としては、特に限定されず、例えば水；メタノール、エタノール、イソプロパノール等のアルコール等が挙げられる。中和剤としては、特に限定されず、例えばステアリン酸、オレイン酸、バーサチック酸等のカルボン酸；無機酸の水溶液、炭酸ガス等が挙げられる。 After performing the denaturation reaction, a deactivator, a neutralizing agent and the like may be added to the reaction solution as necessary. The quenching agent is not particularly limited, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol. The neutralizing agent is not particularly limited, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.
さらに、重合後のゲル生成を防止する観点や、加工時の安定性を向上させる観点から、得られた変性共役ジエン重合体（Ｃ）に対して、ゴム用安定剤を添加することが好ましい。ゴム用安定剤は、特に限定されず、公知のものを用いることができるが、例えば２，６−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシトルエン（ＢＨＴ）、ｎ−オクタデシル−３−（４’−ヒドロキシ−３’，５’−ジ−ｔｅｒｔ−ブチルフェノール）プロピネート、２−メチル−４，６−ビス［（オクチルチオ）メチル］フェノール等の酸化防止剤が好ましい。 Furthermore, it is preferable to add a stabilizer for rubber to the resulting modified conjugated diene polymer (C) from the viewpoint of preventing gel formation after polymerization and improving the stability during processing. The stabilizer for rubber is not particularly limited, and a known stabilizer can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4′- Antioxidants such as hydroxy-3 ′, 5′-di-tert-butylphenol) propinate and 2-methyl-4,6-bis [(octylthio) methyl] phenol are preferred.
変性共役ジエン重合体（Ｃ）を、重合体溶液から取得する方法としては、公知の方法を用いることができる。例えばスチームストリッピング等で溶媒を分離した後、重合体を濾別し、さらにそれを脱水及び乾燥して重合体を取得する方法、フラッシングタンクで濃縮し、さらにベント押し出し機等で脱揮する方法、ドラムドライヤー等で直接脱揮する方法等が挙げられる。 As a method for obtaining the modified conjugated diene polymer (C) from the polymer solution, a known method can be used. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, and the polymer is further dehydrated and dried to obtain the polymer. The method is concentrated in a flushing tank and further devolatilized by a vent extruder or the like. And a method of directly devolatilizing with a drum dryer or the like.
変性共役ジエン重合体（Ｃ）は、必要に応じて、シリカ系無機充填剤やカーボンブラック等の無機充填剤；変性共役ジエン重合体（Ｃ）以外のゴム状重合体；シランカップリング剤及びゴム用軟化剤等を添加した変性共役ジエン重合体組成物として使用することができる。 The modified conjugated diene polymer (C) is an inorganic filler such as a silica-based inorganic filler or carbon black; a rubbery polymer other than the modified conjugated diene polymer (C); a silane coupling agent and a rubber, if necessary. It can be used as a modified conjugated diene polymer composition to which a softener and the like are added.
変性共役ジエン重合体（Ｃ）に、シリカ系無機充填剤を分散させることで、後述するような加硫物としたときに、低ヒステリシスロス性とウェットスキッド抵抗性とのバランスに優れ、かつ実用上十分な耐摩耗性や破壊強度を有し、優れた引っ張り特性を付与できる。なお、変性共役ジエン重合体（Ｃ）を含む変性共役ジエン重合体組成物は、タイヤに用いる場合だけでなく、防振ゴム等の自動車部品、靴等の加硫ゴム用途に用いられる場合にも、シリカ系無機充填剤を含むことが好ましい。 Dispersing the silica-based inorganic filler in the modified conjugated diene polymer (C) provides an excellent balance between low hysteresis loss and wet skid resistance when used as a vulcanizate as described below. In addition, it has sufficient wear resistance and breaking strength, and can impart excellent tensile properties. The modified conjugated diene polymer composition containing the modified conjugated diene polymer (C) is used not only for tires but also for vulcanized rubber applications such as anti-vibration rubber and other automotive parts and shoes. It is preferable that a silica-based inorganic filler is included.
シリカ系無機充填剤としては、特に限定されず、公知のものを用いることができるが、ＳｉＯ2、又はＳｉ3Ａｌを構成単位として含む固体粒子が好ましく、ＳｉＯ2、又はＳｉ3Ａｌを構成単位の主成分とすることがより好ましい。具体的には、シリカ、クレイ、タルク、マイカ、珪藻土、ウォラストナイト、モンモリロナイト、ゼオライト、ガラス繊維等の無機繊維状物質等が挙げられる。また、表面を疎水化したシリカ系無機充填剤や、シリカ系無機充填剤とシリカ系以外の無機充填剤との混合物も用いることができる。これらの中でも、強度や耐摩耗性等の観点から、シリカ及びガラス繊維が好ましく、シリカがより好ましい。シリカとしては、乾式シリカ、湿式シリカ、合成ケイ酸塩シリカ等が挙げられる。これらの中でも、破壊特性の改良効果及びウェットスキッド抵抗性のバランスに優れる観点から、湿式シリカが好ましい。 The silica-based inorganic filler is not particularly limited, but may be a known, SiO 2, or Si 3 solid particles preferably contains Al as a constituent unit, SiO 2, or Si 3 Al constituent units It is more preferable to use as a main component. Specific examples include inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, and the like. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable from the viewpoint of an excellent balance between the effect of improving fracture characteristics and wet skid resistance.
変性共役ジエン重合体組成物におけるシリカ系無機充填剤の配合量は、変性共役ジエン重合体（Ｃ）を含むゴム成分１００質量部に対し、０．５〜３００質量部であることが好ましく、５〜２００質量部がより好ましく、２０〜１００質量部が更に好ましい。シリカ系無機充填剤の配合量は、無機充填剤の添加効果が発現する観点から、０．５質量部以上とすることが好ましく、一方、無機充填剤を十分に分散させ、組成物の引っ張り特性や機械強度を実用的に十分なものとする観点から、３００質量部以下とすることが好ましい。 The blending amount of the silica-based inorganic filler in the modified conjugated diene polymer composition is preferably 0.5 to 300 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (C). -200 mass parts is more preferable, and 20-100 mass parts is still more preferable. The compounding amount of the silica-based inorganic filler is preferably 0.5 parts by mass or more from the viewpoint of manifesting the addition effect of the inorganic filler, while the inorganic filler is sufficiently dispersed, and the tensile properties of the composition And from the viewpoint of making the mechanical strength practically sufficient, it is preferably 300 parts by mass or less.
変性共役ジエン重合体組成物には、カーボンブラックを含有させてもよい。カーボンブラックとしては、特に限定されず、例えばＳＲＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ等の各クラスのカーボンブラックが使用できる。これらの中でも、窒素吸着比表面積が５０ｍ2／ｇ以上、ジブチルフタレート（ＤＢＰ）吸油量が８０ｍＬ／１００ｇのカーボンブラックが好ましい。 The modified conjugated diene polymer composition may contain carbon black. The carbon black is not particularly limited, and for example, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m 2 / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g is preferable.
カーボンブラックの配合量は、変性共役ジエン重合体（Ｃ）を含むゴム成分１００質量部に対し、０．５〜１００質量部が好ましく、３〜１００質量部がより好ましく、５〜５０質量部が更に好ましい。カーボンブラックの配合量は、ドライグリップ性能や導電性等のタイヤ等の用途に求められる性能を発現する観点から、０．５質量部以上とすることが好ましく、その分散性の観点から、１００質量部以下とすることが好ましい。 The compounding amount of carbon black is preferably 0.5 to 100 parts by mass, more preferably 3 to 100 parts by mass, and 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (C). Further preferred. The blending amount of carbon black is preferably 0.5 parts by mass or more from the viewpoint of expressing performances required for applications such as tires such as dry grip performance and conductivity, and 100 masses from the viewpoint of dispersibility. Part or less.
変性共役ジエン重合体組成物には、シリカ系無機充填剤やカーボンブラック以外に、金属酸化物や金属水酸化物を含有させてもよい。金属酸化物とは、化学式ＭxＯy（Ｍは金属原子を表し、ｘ及びｙは各々１〜６の整数を表す。）を構成単位の主成分とする固体粒子のことをいい、例えばアルミナ、酸化チタン、酸化マグネシウム、酸化亜鉛等を用いることができる。また金属酸化物と金属酸化物以外の無機充填剤の混合物も用いることができる。金属水酸化物としては、特に限定されず、例えば水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム等が挙げられる。 In addition to the silica-based inorganic filler and carbon black, the modified conjugated diene polymer composition may contain a metal oxide or a metal hydroxide. Metal oxide refers to solid particles having the chemical formula M x O y (M represents a metal atom, and x and y each represent an integer of 1 to 6) as a main component of a structural unit, such as alumina. , Titanium oxide, magnesium oxide, zinc oxide, and the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used. The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.
変性共役ジエン重合体組成物には、シランカップリング剤を含有させてもよい。シランカップリング剤は、変性共役ジエン重合体（Ｃ）等のゴム成分とシリカ系無機充填剤との相互作用を緊密にする機能を有しており、ゴム成分及びシリカ系無機充填剤のそれぞれに対する親和性又は結合性の基を有しており、一般的には、硫黄結合部分とアルコキシシリル基、シラノール基部分を一分子中に有する化合物が用いられる。具体的には、ビス−［３−（トリエトキシシリル）−プロピル］−テトラスルフィド、ビス−［３−（トリエトキシシリル）−プロピル］−ジスルフィド、ビス−［２−（トリエトキシシリル）−エチル］−テトラスルフィド等が挙げられる。 シランカップリング剤の配合量は、上述したシリカ系無機充填剤１００質量部に対して、０．１〜３０質量部が好ましく、０．５〜２０質量部がより好ましく、１〜１５質量部が更に好ましい。シランカップリング剤の配合量が上記範囲であると、シランカップリング剤による上記添加効果を一層顕著なものにできる。 The modified conjugated diene polymer composition may contain a silane coupling agent. The silane coupling agent has a function to make the interaction between the rubber component such as the modified conjugated diene polymer (C) and the silica-based inorganic filler close to each of the rubber component and the silica-based inorganic filler. A compound having an affinity or binding group and generally having a sulfur bond portion, an alkoxysilyl group, and a silanol group portion in one molecule is used. Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl ] -Tetrasulfide etc. are mentioned. 0.1-30 mass parts is preferable with respect to 100 mass parts of silica type inorganic fillers mentioned above, as for the compounding quantity of a silane coupling agent, 0.5-20 mass parts is more preferable, and 1-15 mass parts is. Further preferred. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent can be made more remarkable.
変性共役ジエン重合体組成物には、加工性の改良を図るために、ゴム用軟化剤を含有させてもよい。ゴム用軟化剤としては、鉱物油、又は液状若しくは低分子量の合成軟化剤が好適である。ゴムの軟化、増容、加工性の向上を図るために使用されているプロセスオイル又はエクステンダーオイルと呼ばれる鉱物油系ゴム用軟化剤は、芳香族環、ナフテン環、及びパラフィン鎖の混合物であり、パラフィン鎖の炭素数が全炭素中５０％以上を占めるものがパラフィン系と呼ばれ、ナフテン環炭素数が３０〜４５％のものがナフテン系、芳香族炭素数が３０％を超えるものが芳香族系と呼ばれている。変性共役ジエン−芳香族ビニル共重合体とともに用いるゴム用軟化剤としては、適度な芳香族含量を有するものが共重合体との馴染みがよい傾向にあるため好ましい。
ゴム用軟化剤の配合量は、変性共役ジエン重合体（Ｃ）を含有するゴム成分１００質量部に対して、０〜１００質量部が好ましく、１０〜９０質量部がより好ましく、３０〜９０質量部が更に好ましい。ゴム用軟化剤の配合量がゴム成分１００質量部に対して１００質量部を超えると、ブリードアウトを生じやすく、組成物表面にベタツキを生ずるおそれがある。
In order to improve processability, the modified conjugated diene polymer composition may contain a rubber softener. As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable. The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system. As the rubber softener used together with the modified conjugated diene-aromatic vinyl copolymer, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.
The blending amount of the rubber softener is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and more preferably 30 to 90 parts by weight with respect to 100 parts by weight of the rubber component containing the modified conjugated diene polymer (C). Part is more preferred. If the blending amount of the rubber softener exceeds 100 parts by mass with respect to 100 parts by mass of the rubber component, bleeding out tends to occur, and the composition surface may become sticky.
変性共役ジエン重合体組成物には、目的を損なわない範囲内で、上述した以外のその他の軟化剤や充填剤、さらに、耐熱安定剤、帯電防止剤、耐候安定剤、老化防止剤、着色剤、滑剤等の各種添加剤を用いてもよい。その他の軟化剤としては、公知の軟化剤を用いることができる。その他の充填剤としては、具体的には、炭酸カルシウム、炭酸マグネシウム、硫酸アルミニウム、硫酸バリウム等が挙げられる。上記の耐熱安定剤、帯電防止剤、耐候安定剤、老化防止剤、着色剤、潤滑剤としては、それぞれ公知の材料を用いることができる。 The modified conjugated diene polymer composition includes other softening agents and fillers other than those described above within a range not impairing the purpose, and further, a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, an antiaging agent, and a coloring agent. Various additives such as a lubricant may be used. As other softeners, known softeners can be used. Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Known materials can be used as the above heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant.
変性共役ジエン重合体（Ｃ）とその他のゴム状重合体、シリカ系無機充填剤、カーボンブラックやその他の充填剤、シランカップリング剤、ゴム用軟化剤及びその他添加剤等を混合して、変性共役ジエン重合体組成物を調製する方法については特に限定されるものではない。
例えばオープンロール、バンバリーミキサー、ニーダー、単軸スクリュー押出機、２軸スクリュー押出機、多軸スクリュー押出機等の一般的な混和機を用いた溶融混練方法、各成分を溶解混合後、溶剤を加熱除去する方法等が挙げられる。これらのうち、ロール、バンバリーミキサー、ニーダー、押出機による溶融混練法が生産性、良混練性の観点から好ましい。また、変性共役ジエン重合体と各種配合剤とを一度に混練する方法、複数の回数に分けて混合する方法のいずれも適用可能である。
The modified conjugated diene polymer (C) and other rubbery polymers, silica inorganic fillers, carbon black and other fillers, silane coupling agents, rubber softeners and other additives are mixed to modify The method for preparing the conjugated diene polymer composition is not particularly limited.
For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., each component is dissolved and mixed, and then the solvent is heated The method of removing etc. are mentioned. Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties. In addition, any of a method of kneading the modified conjugated diene polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.
変性共役ジエン重合体（Ｃ）やこれを含む変性共役ジエン重合体組成物は、加硫物の形で用いるのに適している。加硫物は、例えば変性共役ジエン重合体（Ｃ）又は前述した変性共役ジエン重合体組成物を、加硫剤及び必要に応じて加硫促進剤・助剤等と混合した後、加熱して加硫することにより得ることができる。これらの中でも、変性共役ジエン重合体（Ｃ）を含むゴム成分と、シリカ系無機充填剤とを含む変性共役ジエン重合体組成物を加硫することが好ましい。この場合、変性共役ジエン重合体組成物は、上述した変性共役ジエン重合体（Ｃ）を２０質量部以上含むゴム成分１００質量部と、シリカ系無機充填剤０．５〜３００質量部と、を含むものがより好ましい。 The modified conjugated diene polymer (C) and the modified conjugated diene polymer composition containing the same are suitable for use in the form of a vulcanizate. The vulcanized product is prepared by mixing, for example, the modified conjugated diene polymer (C) or the modified conjugated diene polymer composition described above with a vulcanizing agent and, if necessary, a vulcanization accelerator / auxiliary agent, and the like. It can be obtained by vulcanization. Among these, it is preferable to vulcanize the modified conjugated diene polymer composition containing the rubber component containing the modified conjugated diene polymer (C) and the silica-based inorganic filler. In this case, the modified conjugated diene polymer composition comprises 100 parts by mass of a rubber component containing 20 parts by mass or more of the above-described modified conjugated diene polymer (C), and 0.5 to 300 parts by mass of a silica-based inorganic filler. The inclusion is more preferable.
加硫剤としては、例えば有機過酸化物及びアゾ化合物等のラジカル発生剤、オキシム化合物、ニトロソ化合物、ポリアミン化合物、硫黄、硫黄化合物が使用できる。硫黄化合物には、一塩化硫黄、二塩化硫黄、ジスルフィド化合物、高分子多硫化合物等が含まれる。加硫剤の使用量は、通常は、変性共役ジエン重合体（Ｃ）を含むゴム成分１００質量部に対して０．０１〜２０質量部であり、０．１〜１５質量部が好ましい。加硫方法としては、従来公知の方法を適用でき、加硫温度は、通常１２０〜２００℃、であり、好ましくは１４０〜１８０℃である。 As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like. The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (C). A conventionally known method can be applied as the vulcanization method, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.
また、加硫に際しては、必要に応じて加硫促進剤を用いてもよい。加硫促進剤としては、従来公知の材料を用いることができ、例えばスルフェンアミド系、グアニジン系、チウラム系、アルデヒド−アミン系、アルデヒド−アンモニア系、チアゾール系、チオ尿素系、ジチオカルバメート系等の加硫促進剤が挙げられる。また、加硫助剤としては、亜鉛華、ステアリン酸等を使用できる。加硫促進剤の使用量は、通常、変性共役ジエン重合体（Ｃ）を含むゴム成分１００質量部に対して０．０１〜２０質量部であり、０．１〜１５質量部が好ましい。 In vulcanization, a vulcanization accelerator may be used as necessary. As the vulcanization accelerator, conventionally known materials can be used, for example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate, etc. And vulcanization accelerators. Further, as the vulcanization aid, zinc white, stearic acid or the like can be used. The usage-amount of a vulcanization accelerator is 0.01-20 mass parts normally with respect to 100 mass parts of rubber components containing a modified conjugated diene polymer (C), and 0.1-15 mass parts is preferable.
以下の実施例により本発明を更に詳しく説明する。なお、試料の分析は下記に示す方法により行った。
（１）ムーニー粘度
ＪＩＳ Ｋ６３００に準じて、１１０℃で１分間予熱し、４分後の粘度を測定した。
（２）ＧＰＣ測定
・試料調整：
試料１０ｍｇ及び標準ポリスチレン５ｍｇを２０ｍＬのテトラヒドロフラン（ＴＨＦ）に溶解させた。
・ポリスチレン系カラムＧＰＣ測定条件：
ＴＨＦを溶離液として用い、試料２００μＬを装置に注入して測定した。カラムは、ガードカラム：東ソー ＴＳＫｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ−Ｈ、カラム：東ソー ＴＳＫｇｅｌ Ｇ６０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ５０００ＨＨＲ、ＴＳＫｇｅｌ Ｇ４０００ＨＨＲを使用した。カラムオーブン温度４０℃、ＴＨＦ流量１．０ｍＬ／分の条件で、東ソー製 ＨＬＣ８０２０のＲＩ検出器を用いて測定しクロマトグラムを得た
・シリカ系カラムＧＰＣ測定条件：
ＴＨＦを溶離液として用い、試料２００μＬを装置に注入して測定した。カラムは、デュポン社製：Ｚｏｒｂａｘを使用した。カラムオーブン温度４０℃、ＴＨＦ流量０．５ｍＬ／分の条件で、東ソー製 ＨＬＣ８０２０のＲＩ検出器を用いて測定しクロマトグラムを得た。
（３）分子量、分子量分布
ポリスチレン系ゲルを充填剤としたカラムを３本連結したＧＰＣ測定装置を使用して、クロマトグラムを測定し、標準ポリスチレンを使用した検量線に基づいて重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）、分子量分布（Ｍｗ／Ｍｎ）を求めた。
（４）変性率
シリカ系ゲルを充填剤としたＧＰＣカラムに変性した成分が吸着する特性を応用することにより測定した。試料及び低分子量内部標準ポリスチレンを含む試料溶液を、ポリスチレン系ゲルカラムで測定したクロマトグラムと、シリカ系カラムで測定したクロマトグラムの差分よりシリカカラムへの吸着量を測定し変性率を求めた。
・変性率の計算方法：
ポリスチレン系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料のピーク面積をＰ１、標準ポリスチレンのピーク面積をＰ２、シリカ系カラムを用いたクロマトグラムのピーク面積の全体を１００として、試料の面積をＰ３、標準ポリスチレンのピーク面積をＰ４として、下記式より変性率（％）を求めた。
変性率（％）＝［１−（Ｐ２×Ｐ３）／（Ｐ１×Ｐ４）］×１００
（ただし、Ｐ１＋Ｐ２＝Ｐ３＋Ｐ４＝１００）
The following examples further illustrate the present invention. The sample was analyzed by the method shown below.
(1) Mooney viscosity According to JIS K6300, preheating was performed at 110 ° C. for 1 minute, and the viscosity after 4 minutes was measured.
(2) GPC measurement and sample preparation:
10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of tetrahydrofuran (THF).
-Polystyrene column GPC measurement conditions:
Using THF as an eluent, 200 μL of sample was injected into the apparatus for measurement. As the column, guard column: Tosoh TSKguardcolumn HHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR were used. A chromatogram was obtained by measurement using a Tosoh HLC8020 RI detector at a column oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. Silica-based column GPC measurement conditions:
Using THF as an eluent, 200 μL of sample was injected into the apparatus for measurement. The column used was DuPont Zorbax. A chromatogram was obtained by measuring using a RI detector of HLC8020 manufactured by Tosoh under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 0.5 mL / min.
(3) Molecular weight, molecular weight distribution Using a GPC measuring apparatus in which three columns using polystyrene gel as a filler were connected, a chromatogram was measured, and a weight average molecular weight (Mw) based on a calibration curve using standard polystyrene. ), Number average molecular weight (Mn), and molecular weight distribution (Mw / Mn).
(4) Modification rate It measured by applying the characteristic which the component modified | denatured adsorb | sucks to the GPC column which used the silica gel as the filler. A sample solution containing a sample and a low molecular weight internal standard polystyrene was measured for the amount of adsorption on the silica column from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica column, and the modification rate was determined.
・ Method of calculating denaturation rate:
Sample with 100 as the total peak area of the chromatogram using the polystyrene column, P1 as the peak area of the sample, P2 as the peak area of the standard polystyrene, and 100 as the entire peak area of the chromatogram using the silica column The modification ratio (%) was obtained from the following formula, with the area of P3 being P3 and the peak area of standard polystyrene being P4.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)
〔変性共役ジエン重合体（Ｃ）の製造〕
（実施例１）
４枚パドルの撹拌翼を具備する１０Ｌ反応器（Ｌ／Ｄ＝４）を２つ直列に配置し、１基目を重合反応器、２基目を変性反応器とした。
予め、水分等の不純物を除去した、１，３−ブタジエンを２２．０ｇ／分、スチレンを７．１ｇ／分、ｎ−ヘキサンを１４４ｇ／分の条件で混合し、更に不純物不活性化処理用として、１基目反応器に入る直前でｎ−ブチルリチウム（処理ｎ−ブチルリチウム）０．０８４ｍｍｏｌ／分とスタティックミキサーで混合した後、１基目反応器の底部に連続的に供給し、更に、極性物質として２，２−ビス（２−オキソラニル）プロパンを０．０４０ｇ／分の速度で、重合開始剤としてｎ−ブチルリチウムを０．３５０ｍｍｏｌ／分の速度で、１基目反応器底部へ供給し、反応器出口の内温を９０℃となるように重合反応を継続させ共役ジエン重合体（Ａ）を製造した。
１基目から押出された共役ジエン重合体（Ａ）を含む重合溶液を、そのまま２基目に供給した。２基目の反応器の温度を８５℃に保ち、アルコキシシリル基を有する変性剤（Ｂ）として２，２−ジメトキシ−１−（３−トリメトキシシリルプロピル）−１−アザ−２−シラシクロペンタン（以下、「Ｍ１」という。）を０．０４６ｍｍｏｌ／分の速度で２基目反応器の底部から添加し、変性（カップリング）反応を実施した。２基目反応器の撹拌速度を調整することによって反応器内部における撹拌動力を２５ｋＷ／ｍ３とした。
２基目反応器内の液面高さが反応器全体の７０％となるように反応液を流出し、その流出液に酸化防止剤（ＢＨＴ）をポリマー１００ｇあたり０．２ｇとなるように０．０４８ｇ／分（ｎ−ヘキサン溶液）で連続的に添加し、変性反応を終了させ、その後溶媒を除去し、変性共役ジエン重合体（Ｃ）を得た。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
[Production of Modified Conjugated Diene Polymer (C)]
Example 1
Two 10 L reactors (L / D = 4) equipped with four paddle stirring blades are arranged in series, and the first one is a polymerization reactor and the second is a denaturing reactor.
Preliminary impurities such as moisture, 1,3-butadiene, 22.0 g / min, styrene, 7.1 g / min, n-hexane, 144 g / min. As follows, n-butyllithium (treated n-butyllithium) 0.084 mmol / min was mixed with a static mixer immediately before entering the first reactor, and then continuously fed to the bottom of the first reactor, 2,2-bis (2-oxolanyl) propane as a polar substance at a rate of 0.040 g / min and n-butyllithium as a polymerization initiator at a rate of 0.350 mmol / min to the bottom of the first reactor The conjugated diene polymer (A) was produced by continuing the polymerization reaction so that the internal temperature at the outlet of the reactor was 90 ° C.
The polymerization solution containing the conjugated diene polymer (A) extruded from the first group was supplied as it was to the second group. The temperature of the second reactor was kept at 85 ° C., and 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclo was used as the modifying agent (B) having an alkoxysilyl group. Pentane (hereinafter referred to as “M1”) was added from the bottom of the second reactor at a rate of 0.046 mmol / min to carry out a modification (coupling) reaction. The stirring power in the reactor was adjusted to 25 kW / m 3 by adjusting the stirring speed of the second reactor.
The reaction solution was flowed out so that the liquid level in the second reactor would be 70% of the whole reactor, and 0 gram of antioxidant (BHT) was added to the effluent to make 0.2 g per 100 g of polymer. 0.048 g / min (n-hexane solution) was continuously added to terminate the modification reaction, and then the solvent was removed to obtain a modified conjugated diene polymer (C). The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
（実施例２）
２基目反応器の撹拌速度を変更し、撹拌動力を１０ｋＷ／ｍ３とした他は実施例１と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
（実施例３）
アルコキシシリル基を有する変性剤（Ｂ）として、２，２−ジメトキシ−１−（３−トリメトキシシリルプロピル）−１−アザ−２−シラシクロペンタンを１−［３−（トリエトキシシリル）プロピル］−４−メチルピペラジン（以下、「Ｍ２」という。）とした他は実施例１と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
（実施例４）
２基目反応器の撹拌速度を変更し、撹拌動力を１０ｋＷ／ｍ３とした他は実施例３と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
(Example 2)
The same procedure as in Example 1 was performed except that the stirring speed of the second reactor was changed and the stirring power was changed to 10 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
(Example 3)
As the modifying agent (B) having an alkoxysilyl group, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane is replaced with 1- [3- (triethoxysilyl) propyl. The same procedure as in Example 1 was conducted except that 4-methylpiperazine (hereinafter referred to as “M2”) was used. The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
Example 4
The same procedure as in Example 3 was performed except that the stirring speed of the second reactor was changed and the stirring power was changed to 10 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
（実施例５）
内容積１０リットル（Ｌ／Ｄ＝４）で、４枚パドルの撹拌翼を具備する温度制御が可能なオートクレーブを反応器として使用し、予め不純物を除去したブタジエン６６０ｇ、スチレン２１０ｇ、ノルマルヘキサン４３２０ｇ、極性物質として２，２−ビス（２−オキソラニル）プロパン０．８５ｇを反応器へ入れ、反応器内の温度を４２℃に保持した。
ブチルリチウム１０．５ｍｍｏｌを反応器に供給して、反応を開始した。
反応開始後、重合による発熱で、反応器内の温度は上昇を始め、１２分後に反応器内の温度は最高温度８０℃に達した。
重合反応終了後、反応器にテトラグリシジル−１，３−ビスアミノメチルシクロヘキサン（以下、「Ｍ３」という。）０．４５ｍｍｏｌを添加して、７０℃の温度条件で３分間反応させた後、５．３ｍｍｏｌのＭ２を加えて３分間変性反応を実施した。この時の撹拌翼の回転数を調整して撹拌動力が１５ｋＷ／ｍ３となるようにした。この反応溶液に酸化防止剤（２，６−ジ−ｔ−ブチル−ｐ−クレゾール：ＢＨＴ）２．１ｇを添加した後、スチームストリッピングにより溶媒を除去し、乾燥機により乾燥処理を施して、変性成分を含むスチレン−ブタジエン共重合体を得た。得られた変性共役ジエン重合体（Ｃ）の分析結果を表３に、これを含むゴム組成物の評価結果を表４に示す。
示す。
(Example 5)
Using an autoclave with an internal volume of 10 liters (L / D = 4) and a four-paddle stirring blade capable of temperature control as a reactor, 660 g of butadiene from which impurities were previously removed, 210 g of styrene, 4320 g of normal hexane, As a polar substance, 0.85 g of 2,2-bis (2-oxolanyl) propane was charged into the reactor, and the temperature in the reactor was maintained at 42 ° C.
10.5 mmol of butyl lithium was supplied to the reactor to initiate the reaction.
After the start of the reaction, the temperature in the reactor started to rise due to heat generated by polymerization, and after 12 minutes, the temperature in the reactor reached a maximum temperature of 80 ° C.
After completion of the polymerization reaction, 0.45 mmol of tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter referred to as “M3”) was added to the reactor and reacted at a temperature condition of 70 ° C. for 3 minutes. .3 mmol of M2 was added and the denaturation reaction was carried out for 3 minutes. The number of revolutions of the stirring blade at this time was adjusted so that the stirring power was 15 kW / m 3 . After adding 2.1 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this reaction solution, the solvent is removed by steam stripping, and a drying treatment is performed by a dryer. A styrene-butadiene copolymer containing a modifying component was obtained. The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 3, and the evaluation results of the rubber composition containing the same are shown in Table 4.
Show.
（実施例６）
アルコキシシリル基を有する変性剤（Ｂ）として、Ｍ２の代わりにＭ１を用いた他は実施例５と同様にして、変性共役ジエン重合体（Ｃ）を製造した。得られた変性共役ジエン重合体（Ｃ）の分析結果を表３に、これを含むゴム組成物の評価結果を表４に示す。
(Example 6)
A modified conjugated diene polymer (C) was produced in the same manner as in Example 5 except that M1 was used instead of M2 as the modifier (B) having an alkoxysilyl group. The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 3, and the evaluation results of the rubber composition containing the same are shown in Table 4.
（比較例１）
変性反応器内の撹拌動力を０．７ｋＷ／ｍ３とした他は実施例１と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
（比較例２）
変性反応時の撹拌動力を０．５ｋＷ／ｍ３とした他は実施例３と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表１に、これを含むゴム組成物の評価結果を表２に示す。
（比較例３）
変性反応を行う時の撹拌動力を０．５ｋＷ／ｍ３とした他は実施例５と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表３に、これを含むゴム組成物の評価結果を表４に示す。
（比較例４）
変性反応を行う時の撹拌動力を０．５ｋＷ／ｍ３とした他は実施例６と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表３に、これを含むゴム組成物の評価結果を表４に示す。
（比較例５）
変性反応を行う時の撹拌動力を７０ｋＷ／ｍ３とした他は実施例１と同様に行った。得られた変性共役ジエン重合体（Ｃ）の分析結果を表３に、これを含むゴム組成物の評価結果を表４に示す。
(Comparative Example 1)
The same procedure as in Example 1 was conducted except that the stirring power in the denaturation reactor was 0.7 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
(Comparative Example 2)
The same procedure as in Example 3 was performed except that the stirring power during the denaturing reaction was changed to 0.5 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 1, and the evaluation results of rubber compositions containing the same are shown in Table 2.
(Comparative Example 3)
The same procedure as in Example 5 was performed except that the stirring power during the denaturation reaction was changed to 0.5 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 3, and the evaluation results of the rubber composition containing the same are shown in Table 4.
(Comparative Example 4)
The same procedure as in Example 6 was performed except that the stirring power during the denaturation reaction was 0.5 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 3, and the evaluation results of the rubber composition containing the same are shown in Table 4.
(Comparative Example 5)
The same procedure as in Example 1 was performed except that the stirring power during the denaturation reaction was set to 70 kW / m 3 . The analysis results of the resulting modified conjugated diene polymer (C) are shown in Table 3, and the evaluation results of the rubber composition containing the same are shown in Table 4.
〔ゴム組成物の製造と特性評価〕
実施例及び比較例において得られた変性共役ジエン重合体（Ｃ）を含むゴム組成物は、表５に示すような配合で、以下に示す方法で製造した。
温度制御装置を具備する密閉混練機（内容量０．３リットル）を使用し、第一段の混練として、充填率６５％、ローター回転数５０／５７ｒｐｍの条件で、原料ゴム（変性共役ジエン重合体（Ｃ））、充填剤（シリカ、カーボンブラック）、有機シランカップリング剤、プロセスオイル（伸展油）、亜鉛華、ステアリン酸を混練した。このとき、密閉混合機の温度を制御し、排出温度（配合物）は１５５〜１６０℃でゴム組成物を得た。
次に、第二段の混練として、上記で得た配合物を室温まで冷却後、老化防止剤を加え、シリカの分散を向上させるため再度混練した。この場合も、混合機の温度制御により排出温度（配合物）を１５５〜１６０℃に調整した。
冷却後、第三段の混練として、７０℃に設定したオープンロールにて、硫黄、加硫促進剤を加えて混練した。その後、成型し、１６０℃で２０分間、加硫プレスにて加硫した。加硫後、ゴム組成物の物性を測定した。
[Production and characteristic evaluation of rubber composition]
The rubber composition containing the modified conjugated diene polymer (C) obtained in Examples and Comparative Examples was prepared by the method shown below with the formulation shown in Table 5.
Using a closed kneading machine (with an internal volume of 0.3 liters) equipped with a temperature control device, the raw rubber (modified conjugated diene weight) was used as the first stage kneading under the conditions of a filling rate of 65% and a rotor rotational speed of 50/57 rpm. Combined (C)), filler (silica, carbon black), organosilane coupling agent, process oil (extended oil), zinc white, and stearic acid were kneaded. At this time, the temperature of the closed mixer was controlled, and the rubber composition was obtained at a discharge temperature (compound) of 155 to 160 ° C.
Next, as the second stage kneading, the blend obtained above was cooled to room temperature, an anti-aging agent was added, and kneaded again to improve silica dispersion. Also in this case, the discharge temperature (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
After cooling, as a third stage of kneading, sulfur and a vulcanization accelerator were added and kneaded with an open roll set at 70 ° C. Thereafter, it was molded and vulcanized with a vulcanization press at 160 ° C. for 20 minutes. After vulcanization, the physical properties of the rubber composition were measured.
実施例及び比較例において得られた変性共役ジエン重合体（Ｃ）を含むゴム組成物の各物性は、下記に示す方法により測定した。
＜粘弾性パラメータ（ｔａｎδ）＞
レオメトリックス・サイエンティフィック社製の粘弾性試験機（ＡＲＥＳ）を使用し、ねじりモードで加硫試験片の粘弾性パラメータを測定した。
０℃において周波数１０Ｈｚ、ひずみ１％で測定したｔａｎδをウェットグリップ性能の指標とした。指数値が大きいほどウェットスキッド抵抗性が良好であることを示す。
また５０℃において周波数１０Ｈｚ、ひずみ３％で測定したｔａｎδを省燃費特性の指標とした。指数値の小さいほど低ヒステリシスロス性が良好であることを示す。
＜耐摩耗性＞
アクロン摩耗試験機を使用し、ＪＩＳ Ｋ６２６４−２に従って、荷重４４．１Ｎ、１０００回転での加硫試験片の摩耗量を測定し、指数化した。
指数値の大きいほど耐摩耗性が優れることを示す。
＜引っ張り伸び率＞
加硫試験片を、ＪＩＳ Ｋ６２５１の引張試験法により測定した。指数値が大きいほど耐破壊性に優れることを示す。
Each physical property of the rubber composition containing the modified conjugated diene polymer (C) obtained in Examples and Comparative Examples was measured by the following methods.
<Viscoelastic parameter (tan δ)>
Using a viscoelasticity tester (ARES) manufactured by Rheometrics Scientific, the viscoelastic parameters of the vulcanized specimens were measured in torsion mode.
Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. It shows that wet skid resistance is so favorable that an index value is large.
Further, tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. It shows that low hysteresis loss property is so favorable that an index value is small.
<Abrasion resistance>
Using an Akron abrasion tester, according to JIS K6264-2, the wear amount of the vulcanized test piece at a load of 44.1 N and 1000 revolutions was measured and indexed.
It shows that abrasion resistance is excellent, so that an index value is large.
<Tensile elongation>
The vulcanized test piece was measured by the tensile test method of JIS K6251. The larger the index value, the better the fracture resistance.
上記、変性反応時の撹拌動力を１〜５０ｋＷ／ｍ３の範囲内にした実施例では、変性剤Ｍ１，Ｍ２のいずれを用いた場合にも高い変性率で変性共役ジエン重合体（Ｃ）を得ることができ、これらをシリカ等と配合することにより低ヒステリシスロス性とウェットスキッド抵抗性、引っ張り特性、耐摩耗性のバランスに優れたゴム組成物を得ることができた。
これに対して、変性反応時の攪拌動力が大きすぎても（比較例５）、小さすぎても（比較例１〜４）、共役ジエン重合体（Ａ）の変性率は十分でなく、その結果、得られたゴム組成物は、耐摩耗性、引っ張り特性、ウェットスキッド抵抗性及び低ヒステリシスロス性のバランスに劣る。
In the above-described examples in which the stirring power during the modification reaction is within the range of 1 to 50 kW / m 3 , the modified conjugated diene polymer (C) is obtained with a high modification rate even when any of the modifiers M1 and M2 is used. By blending these with silica or the like, it was possible to obtain a rubber composition excellent in the balance of low hysteresis loss, wet skid resistance, tensile properties, and abrasion resistance.
On the other hand, even if the stirring power during the modification reaction is too large (Comparative Example 5) or too small (Comparative Examples 1 to 4), the modification rate of the conjugated diene polymer (A) is not sufficient. As a result, the obtained rubber composition is inferior in the balance of abrasion resistance, tensile properties, wet skid resistance and low hysteresis loss.
本発明の製造方法で得られる変性共役ジエン重合体（Ｃ）を無機充填剤と組み合わせたゴム組成物は、自動車の内装・外装品、防振ゴム、ベルト、はきもの、発泡体、各種工業部品、タイヤ用途等に好適に使用することができる。
とりわけ、本発明の製造方法で得られる変性共役ジエン重合体（Ｃ）を無機充填剤と組み合わせたゴム組成物は、低ヒステリシスロス性及びウエットスキッド抵抗性に優れているため、タイヤに好適に使用できる。
The rubber composition obtained by combining the modified conjugated diene polymer (C) obtained by the production method of the present invention with an inorganic filler is used for automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, various industrial parts. It can be suitably used for tire applications and the like.
In particular, the rubber composition obtained by combining the modified conjugated diene polymer (C) obtained by the production method of the present invention with an inorganic filler is excellent in low hysteresis loss and wet skid resistance, and is therefore preferably used for tires. it can.
Claims (7)
前記共役ジエン重合体（Ａ）とアルコキシシリル基を有する変性剤（Ｂ）を混合撹拌し、両者を反応させる変性反応工程を
有する、変性共役ジエン重合体（Ｃ）の製造方法において、
前記変性反応工程における前記攪拌の撹拌動力が１〜５０ｋＷ／ｍ３である変性共役ジエン重合体（Ｃ）の製造方法。 A step of preparing a conjugated diene polymer (A) having an active end, and a modification reaction step of mixing and stirring the conjugated diene polymer (A) and a modifying agent (B) having an alkoxysilyl group and reacting both. In the production method of the modified conjugated diene polymer (C),
The manufacturing method of the modified conjugated diene polymer (C) whose stirring power of the said stirring in the said modification reaction process is 1-50 kW / m < 3 >.
（式中、ＸはＣｌ，Ｂｒ，Ｉのいずれか１つから選ばれ、Ｒ１，Ｒ２はアルキル基、アリール基、ビニル基のいずれか１つ、ｍは１〜４の整数、ｎは１〜３の整数、ｍ＋ｎは２〜４である） The method for producing a modified conjugated diene polymer according to any one of claims 1 to 3, wherein the modifier (B) is a compound represented by the following general formula (1).
(Wherein X is selected from any one of Cl, Br, and I, R 1 and R 2 are any one of an alkyl group, an aryl group, and a vinyl group, m is an integer of 1 to 4, and n is An integer of 1 to 3, m + n is 2 to 4)
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136034A (en) * | 1992-10-26 | 1994-05-17 | Asahi Chem Ind Co Ltd | Method for removing remaining catalyst from conjugated diene-based polymer |
| JPH09208624A (en) * | 1995-11-27 | 1997-08-12 | Kanegafuchi Chem Ind Co Ltd | Production of polymer having functional group |
| JP2002284814A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Production method for modified conjugated diene polymer |
| WO2010044252A1 (en) * | 2008-10-14 | 2010-04-22 | 旭化成ケミカルズ株式会社 | Modified conjugated diene polymer, method for producing the same, modified conjugated diene polymer composition, and tire |
| WO2011129425A1 (en) * | 2010-04-16 | 2011-10-20 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, and composition of modified conjugated diene polymer |
-
2011
- 2011-12-20 JP JP2011278189A patent/JP2013129693A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06136034A (en) * | 1992-10-26 | 1994-05-17 | Asahi Chem Ind Co Ltd | Method for removing remaining catalyst from conjugated diene-based polymer |
| JPH09208624A (en) * | 1995-11-27 | 1997-08-12 | Kanegafuchi Chem Ind Co Ltd | Production of polymer having functional group |
| JP2002284814A (en) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | Production method for modified conjugated diene polymer |
| WO2010044252A1 (en) * | 2008-10-14 | 2010-04-22 | 旭化成ケミカルズ株式会社 | Modified conjugated diene polymer, method for producing the same, modified conjugated diene polymer composition, and tire |
| WO2011129425A1 (en) * | 2010-04-16 | 2011-10-20 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, and composition of modified conjugated diene polymer |
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