JP2005290355A - Modified diene polymer rubber and process for producing the same - Google Patents
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Abstract
【課題】 優れた反撥弾性を有する変性重合体ゴム及びその製造方法を提供する。
【解決手段】 以下の工程から得られる、変性重合体ゴム。ゴム組成物としては、該変性重合体ゴムを、ゴム成分中１０重量％以上含有するものが好ましい。
工程１：アルカリ金属触媒の存在下、炭化水素溶媒中で、共役ジエンモノマー、又は、共役ジエンモノマーと芳香族ビニルモノマーとを重合させ、アルカリ金属末端を有する活性重合体を得る工程、
工程２：該活性重合体と、下式（１）（式中、Ｒ1、Ｒ2およびＲ3はそれぞれ独立の炭素数１〜４のアルキル基を表し、Ｒ4およびＲ5はそれぞれ独立の炭素数１〜６のアルキル基を表し、ｎは０または１〜１０の整数を表す）で表される化合物とを反応させて、変性重合体ゴムを得る工程。
【選択図】 なしPROBLEM TO BE SOLVED: To provide a modified polymer rubber having excellent rebound resilience and a method for producing the same.
A modified polymer rubber obtained from the following steps. As the rubber composition, those containing 10% by weight or more of the modified polymer rubber in the rubber component are preferable.
Step 1: A step of polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an alkali metal catalyst to obtain an active polymer having an alkali metal terminal,
Step 2: The active polymer and the following formula (1) (wherein R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 4 carbon atoms, and R 4 and R 5 are each independently A step of obtaining a modified polymer rubber by reacting with a compound represented by an alkyl group having 1 to 6 carbon atoms, wherein n represents 0 or an integer of 1 to 10.
[Selection figure] None
Description
本発明は、優れた反撥弾性を有する（したがって、優れた省燃費性を有する自動車タイヤを製造し得る）変性重合体ゴム及びその製造方法に関する。 The present invention relates to a modified polymer rubber having excellent rebound resilience (and thus capable of producing an automobile tire having excellent fuel efficiency) and a method for producing the same.
自動車タイヤ用ゴムとして、乳化重合法によって得られるスチレン−ブタジエン共重合体が知られている。しかしながら、該共重合体の反撥弾性は劣っているので、該共重合体からなる自動車タイヤは、優れた省燃費性を持っていないという問題点を有している。
優れた反撥弾性を有するゴムを得るための試みとして、特許文献１には、ブタジエンとスチレンとを、有機リチウム化合物を重合開始剤とし、エ−テルのようなルイス塩基をミクロ構造調節剤とし、炭化水素溶媒中で共重合させる方法が開示されている。
また、特許文献２には、ジエン重合体ゴムのアルカリ金属末端に特定のアクリルアミドを反応させて、反撥弾性の改良された変性ジエン共重合体ゴムを得る方法が提案されている。
As a rubber for automobile tires, a styrene-butadiene copolymer obtained by an emulsion polymerization method is known. However, since the rebound resilience of the copolymer is inferior, the automobile tire made of the copolymer has a problem that it does not have excellent fuel economy.
As an attempt to obtain a rubber having excellent rebound resilience, Patent Document 1 includes butadiene and styrene, an organolithium compound as a polymerization initiator, and a Lewis base such as ether as a microstructure modifier. A method of copolymerizing in a hydrocarbon solvent is disclosed.
Patent Document 2 proposes a method of obtaining a modified diene copolymer rubber having improved rebound resilience by reacting a specific acrylamide with the alkali metal terminal of the diene polymer rubber.
さらに、特許文献３には、ジエン重合体ゴムのアルカリ金属末端にアミノカルビルオキシシランを反応させて、反撥弾性の改良された変性ジエン共重合体ゴムを得る方法が提案されているが、改良レベルには不十分であった。今回さらに検討を重ねた結果、新たに優れた化合物を特定するに至った。 Furthermore, Patent Document 3 proposes a method of obtaining a modified diene copolymer rubber having improved rebound resilience by reacting aminocarbyloxysilane with the alkali metal terminal of the diene polymer rubber. The level was insufficient. As a result of further investigations this time, it came to identify a new excellent compound.
しかしながら近年、自動車タイヤの省燃費性に対する要求は、環境に対する配慮を背景に、一層高度なものとなっており、上記の共重合体ゴムはこの要求に十分に応えることができない。 However, in recent years, the demand for fuel economy of automobile tires has become more sophisticated against the background of environmental considerations, and the above copolymer rubber cannot sufficiently meet this demand.
本発明の目的は、優れた反撥弾性を有する変性重合体ゴム及びその製造方法を提供することにある。 An object of the present invention is to provide a modified polymer rubber having excellent rebound resilience and a method for producing the same.
本発明のうち第一の発明は、以下の工程から得られる、変性重合体ゴムに係るものである。
工程１：アルカリ金属触媒の存在下、炭化水素溶媒中で、共役ジエンモノマー、又は、共役ジエンモノマーと芳香族ビニルモノマーとを重合させ、アルカリ金属末端を有する活性重合体を得る工程、
工程２：該活性重合体と、下式（１）（式中、Ｒ1、Ｒ2およびＲ3はそれぞれ独立の炭素数１〜４のアルキル基を表し、Ｒ4およびＲ5はそれぞれ独立の炭素数１〜６のアルキル基を表し、ｎは０または１〜１０の整数を表す）で表される化合物とを反応させて、変性重合体ゴムを得る工程。
本発明のうち第三の発明は、該変性重合体ゴムを、ゴム成分中１０重量％以上含有するゴム組成物に係るものである。
The first invention of the present invention relates to a modified polymer rubber obtained from the following steps.
Step 1: A step of polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an alkali metal catalyst to obtain an active polymer having an alkali metal terminal,
Step 2: The active polymer and the following formula (1) (wherein R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 4 carbon atoms, and R 4 and R 5 are each independently A step of obtaining a modified polymer rubber by reacting with a compound represented by an alkyl group having 1 to 6 carbon atoms, wherein n represents 0 or an integer of 1 to 10.
The third invention of the present invention relates to a rubber composition containing the modified polymer rubber in an amount of 10% by weight or more in the rubber component.
本発明により、省燃費性に優れた変性ジエン系重合体ゴム、その製造方法及び該重合体ゴムを用いたゴム組成物を提供することができる。 According to the present invention, it is possible to provide a modified diene polymer rubber excellent in fuel efficiency, a method for producing the same, and a rubber composition using the polymer rubber.
本発明で用いられる共役ジエンモノマーとしては、１，３−ブタジエン、イソプレン、１，３−ペンタジエン（ピペリン）、２，３−ジメチル−１，３−ブタジエンおよび１，３−ヘキサジエンを例示することができる。中でも、入手容易性や、得られる変性重合体ゴムの物性の観点から、１，３−ブタジエンやイソプレンが好ましい。 Examples of the conjugated diene monomer used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene. it can. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability and physical properties of the resulting modified polymer rubber.
本発明で用いられる芳香族ビニルモノマーとしては、スチレン、α−メチルスチレン、ビニルトルエン、ビニルナフタレン、ジビニルベンゼン、トリビニルベンゼン、及び、ジビニルナフタレンを例示することができる。中でも、入手容易性や、得られる変性重合体ゴムの物性の観点から、スチレンが好ましい。 Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, and divinyl naphthalene. Among these, styrene is preferable from the viewpoint of availability and the physical properties of the resulting modified polymer rubber.
本発明で用いられる炭化水素溶媒は、アルカリ金属触媒を失活させない溶媒である。適した溶剤として、脂肪族炭化水素、芳香族炭化水素および脂環族炭化水素を例示することができる。特に適した溶媒は炭素数２〜１２の溶媒である。溶媒として、プロパン、ｎ−ブタン、ｉｓｏ−ブタン、ｎ−ペンタン、ｉｓｏ−ペンタン、ｎ−ヘキサン、シクロヘキサン、プロペン、１−ブテン、ｉｓｏ−ブテン、トランス−２−ブテン、シス−２−ブテン、１−ペンテン、２−ペンテン、１−ヘキセン、２−ヘキセン、ベンゼン、トルエン、キシレン、およびエチルベンゼン、ならびに、これらの少なくとも２種の組合せを例示することができる。 The hydrocarbon solvent used in the present invention is a solvent that does not deactivate the alkali metal catalyst. Examples of suitable solvents include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. Particularly suitable solvents are those having 2 to 12 carbon atoms. As a solvent, propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1 -Pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene, and combinations of at least two of these.
本発明で用いられるアルカリ金属触媒として、リチウム、ナトリウム、カリウム、ルビジウムおよびセシウムのような金属や、該金属を含有する炭化水素化合物や、該金属と極性化合物との錯体を例示することができる。中でも、２〜２０個の炭素原子を有するリチウム又はナトリウム化合物が好ましい。 Examples of the alkali metal catalyst used in the present invention include metals such as lithium, sodium, potassium, rubidium and cesium, hydrocarbon compounds containing the metal, and complexes of the metal and a polar compound. Of these, lithium or sodium compounds having 2 to 20 carbon atoms are preferred.
アルカリ金属触媒として、エチルリチウム、ｎ−プロピルリチウム、ｉｓｏ−プロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔ−オクチルリチウム、ｎ−デシルリチウム、フェニルリチウム、２−ナフチルリチウム、２−ブチル−フェニルリチウム、４−フェニル−ブチルリチウム、シクロヘキシルリチウム、４−シクロペンチルリチウム、１，４−ジリチオ−ブテン−２、ナトリウムナフタレン、ナトリウムビフェニル、カリウム−テトラヒドロフラン錯体、カリウムジエトキシエタン錯体、および、α−メチルスチレンテトラマーのナトリウム塩を例示することができる。 As an alkali metal catalyst, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl- Phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, 4-cyclopentyl lithium, 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, and α-methyl A sodium salt of styrene tetramer can be exemplified.
式（１）中、好ましいＲ1、Ｒ2及びＲ3はメチル基、又はエチル基である。Ｒ1、Ｒ2及びＲ3は同じであっても異なってもよいが、すべて同じであるものが製造上好ましい。同式中、好ましいＲ4及びＲ5はメチル基、又はエチル基である。またＲ4及びＲ5は同じであっても異なってもよいが、同じであるものが製造上好ましい。 In the formula (1), preferable R 1, R 2 and R 3 are a methyl group or an ethyl group. R 1, R 2 and R 3 may be the same or different, but are preferably the same for production. In the formula, preferable R 4 and R 5 are a methyl group or an ethyl group. R 4 and R 5 may be the same or different, but the same is preferable for production.
式（１）中、好ましいｎは３又は４である。ｎが０のものは、ｎが３又は４の場合に比較して、得られるゴム組成物の少燃費性が低く、ｎが１及び２のものは製造上、合成が難しい。またｎが５以上の場合には、（１）の分子量が大きくなるため、製造過程において蒸留精製が困難になる。 In the formula (1), preferable n is 3 or 4. When n is 0, the fuel composition obtained is less fuel efficient than when n is 3 or 4, and when n is 1 or 2, synthesis is difficult in production. On the other hand, when n is 5 or more, the molecular weight of (1) becomes large, so that distillation purification becomes difficult in the production process.
式（１）で表される化合物としては、[３−（ジメチルアミノ）プロピル]トリメトキシシラン、[３−（ジエチルアミノ）プロピル]トリメトキシシラン、[３−（ジメチルアミノ）プロピル]トリエトキシシラン、[３−（ジエチルアミノ）プロピル]トリエトキシシラン、[（３−メチル−３−エチルアミノ）プロピル]トリメトキシシラン、[（３−メチル−３−エチルアミノ）プロピル]トリエトキシシラン等を例示することができる。中でも、省燃費性を著しく改良できるという観点から、[３−（ジエチルアミノ）プロピル]トリメトキシシランおよび[３−（ジメチルアミノ）プロピル]トリエトキシシランが好ましい。 Examples of the compound represented by the formula (1) include [3- (dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, Illustrate [3- (diethylamino) propyl] triethoxysilane, [(3-methyl-3-ethylamino) propyl] trimethoxysilane, [(3-methyl-3-ethylamino) propyl] triethoxysilane, and the like. Can do. Among these, [3- (diethylamino) propyl] trimethoxysilane and [3- (dimethylamino) propyl] triethoxysilane are preferable from the viewpoint that fuel economy can be remarkably improved.
本発明において共役ジエンモノマーと芳香族ビニルモノマーとの組合せを用いる場合、共役ジエンモノマー／芳香族ビニルモノマーの重量比は５０／５０〜９０／１０が好ましく、５５／４５〜８５／１５がさらに好ましい。該比が５０／５０未満であると、得られる変性重合体ゴムが炭化水素溶媒に不溶となり、その結果、均一な重合ができない場合がある。該比が９０／１０を超えると、得られる変性重合体ゴムの強度が低下する場合がある。該組合せで得られる共重合体は、省燃費性改良の観点から、ランダム共重合体であることが望ましい。ブロック共重合体の場合には、加硫ゴムとした時の省燃費性が低下することがある。 In the present invention, when a combination of a conjugated diene monomer and an aromatic vinyl monomer is used, the weight ratio of conjugated diene monomer / aromatic vinyl monomer is preferably 50/50 to 90/10, and more preferably 55/45 to 85/15. . When the ratio is less than 50/50, the resulting modified polymer rubber becomes insoluble in the hydrocarbon solvent, and as a result, uniform polymerization may not be possible. When this ratio exceeds 90/10, the strength of the resulting modified polymer rubber may be lowered. The copolymer obtained by the combination is desirably a random copolymer from the viewpoint of improving fuel economy. In the case of a block copolymer, fuel economy may be reduced when a vulcanized rubber is used.
本発明で用いられる共役ジエンモノマーや芳香族ビニルモノマーは、ランダマイザーや、得られる変性重合体ゴム中の、共役ジエンモノマーから誘導されるビニル結合の含有量を調節する化合物と組合せて用いてもよい。本発明における重合様式は、特に制限されない。 The conjugated diene monomer and aromatic vinyl monomer used in the present invention may be used in combination with a randomizer or a compound that adjusts the content of vinyl bonds derived from the conjugated diene monomer in the resulting modified polymer rubber. Good. The polymerization mode in the present invention is not particularly limited.
上記の、ビニル結合の含有量を調節する化合物として、ルイス塩基性化合物を例示することができる。該化合物として、工業的に実施する際の入手容易性の観点から、エーテルまたは第三級アミンが好ましい。 Examples of the compound that adjusts the content of the vinyl bond include Lewis basic compounds. The compound is preferably an ether or a tertiary amine from the viewpoint of easy availability when industrially carried out.
上記エーテルとして、テトラヒドロフラン、テトラヒドロピランおよび１，４−ジオキサンのような環状エーテル；ジエチルエーテルおよびジブチルエーテルのような脂肪族モノエーテル；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エチルエーテル、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エチルエーテル、およびジエチレングリコールジブチルエーテルのような脂肪族ジエ−テル；ならびにジフェニルエーテルおよびアニソールのような芳香族エーテル、を例示することができる。
上記第三級アミンとして、トリエチルアミン、トリプロピルアミン、トリブチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ−ジエチルアニリン、ピリジン、およびキノリンを例示することができる。
Examples of the ether include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether And aliphatic diethers such as diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole.
Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, and quinoline.
式（１）で表される化合物の使用量は、アルカリ金属触媒１モル当たり、通常０．１〜１０モル、好ましくは０．５〜２モルである。該使用量が０．５モル未満であると、省燃費性の改良効果が少なく、２モルを超えると、未反応の式（１）化合物が溶媒中に残存するので、経済的に好ましくない。なぜなら、該溶媒をリサイクルして再使用する場合、該溶媒中の式（１）化合物を分離する工程が必要であるからである。 The usage-amount of the compound represented by Formula (1) is 0.1-10 mol normally with respect to 1 mol of alkali metal catalysts, Preferably it is 0.5-2 mol. If the amount used is less than 0.5 mol, the effect of improving fuel economy is small, and if it exceeds 2 mol, the unreacted compound of formula (1) remains in the solvent, which is economically undesirable. This is because, when the solvent is recycled and reused, a step of separating the compound of the formula (1) in the solvent is necessary.
式（１）で表される化合物と活性重合体との反応は、迅速に進行する。（１）と活性重合体との好ましい接触方法として、工程１で得られる重合反応混合物中に式（１）化合物を添加する方法を例示することができる。 The reaction between the compound represented by the formula (1) and the active polymer proceeds rapidly. As a preferred contact method between (1) and the active polymer, a method of adding the compound of formula (1) to the polymerization reaction mixture obtained in step 1 can be exemplified.
得られる変性重合体ゴムの混練加工性の観点から、式（１）化合物と活性重合体との反応の前または後に、活性重合体に対して下式（式中、Ｒはアルキル基、アルケニル基、シクロアルケニル基または芳香族炭化水素基を表し；Ｍはケイ素原子またはスズ原子を表し；Ｘはハロゲン原子を表し；ａは０〜２の整数を表す）で示されるカップリング剤を添加してもよい。
ＲaＭＸ4-a
From the viewpoint of kneadability of the resulting modified polymer rubber, before or after the reaction between the compound of formula (1) and the active polymer, the active polymer is represented by the following formula (wherein R is an alkyl group, alkenyl group). And a cycloalkenyl group or an aromatic hydrocarbon group; M represents a silicon atom or a tin atom; X represents a halogen atom; a represents an integer of 0 to 2) Also good.
R a MX 4-a
上記カップリング剤の添加量は、アルカリ金属触媒１モル当たり、通常０．０３〜０．４モル、好ましくは０．０５〜０．３モルである。該添加量が０．０３モル未満であると、変性重合体ゴムの加工性の改良効果が少ない。該添加量が０．４モルを超えると、式（１）で表される化合物と反応する活性重合体の割合が少なくなるので、省燃費性の改良効果が低下する。 The amount of the coupling agent added is usually 0.03 to 0.4 mol, preferably 0.05 to 0.3 mol, per mol of the alkali metal catalyst. When the addition amount is less than 0.03 mol, the effect of improving the processability of the modified polymer rubber is small. When the added amount exceeds 0.4 mol, the ratio of the active polymer that reacts with the compound represented by the formula (1) decreases, so that the effect of improving fuel economy is reduced.
工程２で得られる反応混合物中の変性重合体ゴムは、溶液重合法によるゴムの製造において通常実施されている（１）凝固剤を添加する方法、または、（２）スチームを添加する方法のような一般的な凝固法によって、凝固される。凝固温度は特に制限されない。 The modified polymer rubber in the reaction mixture obtained in step 2 is usually used in the production of rubber by a solution polymerization method (1) a method of adding a coagulant or (2) a method of adding steam. It is solidified by a common solidification method. The solidification temperature is not particularly limited.
凝固された変性重合体ゴムは、バンドドライヤーや押出型ドライヤーのような、合成ゴムの製造で用いられている公知の乾燥機で乾燥される。乾燥温度は特に制限されない。 The coagulated modified polymer rubber is dried by a known drier used in the production of synthetic rubber, such as a band drier or an extrusion drier. The drying temperature is not particularly limited.
得られる変性重合体ゴムのムーニー粘度（ＭＬ1+4）は、好ましくは１０〜２００、更に好ましくは２０〜１５０である。該粘度が１０未満であると、その加硫物の引張り強度のような機械物性が低下する場合がある。該粘度が２００を超えると、それを他のゴムと組合せた組成物として使用する場合の混和性が悪化するので加工しにくくなり、その結果、得られるゴム組成物の加硫物の機械物性が低下する場合がある。 The resulting modified polymer rubber has a Mooney viscosity (ML 1 + 4 ) of preferably 10 to 200, more preferably 20 to 150. If the viscosity is less than 10, mechanical properties such as the tensile strength of the vulcanizate may deteriorate. When the viscosity exceeds 200, the miscibility in the case of using it as a composition in combination with other rubber is deteriorated, so that it becomes difficult to process. As a result, the mechanical properties of the vulcanized product of the resulting rubber composition are reduced. May decrease.
得られる変性重合体ゴムの、共役ジエンモノマー単位に由来するビニル結合の含有量は、好ましくは１０〜７０％、更に好ましくは１５〜６０％である。該含有量が１０％未満であると、該重合体ゴムのガラス転移温度が低下し、その結果、該重合体ゴムからなるタイヤのグリップ性能が劣る場合がある。該含有量が７０％を超えると、該重合体ゴムのガラス転移温度が上昇し、その結果、該重合体ゴムの反撥弾性が劣る場合がある。
得られる変性重合体ゴムは、他のゴムや添加剤のような成分と組合せて、組成物として用いてもよい。
The content of the vinyl bond derived from the conjugated diene monomer unit in the modified polymer rubber obtained is preferably 10 to 70%, more preferably 15 to 60%. When the content is less than 10%, the glass transition temperature of the polymer rubber is lowered, and as a result, the grip performance of a tire made of the polymer rubber may be inferior. When the content exceeds 70%, the glass transition temperature of the polymer rubber increases, and as a result, the rebound resilience of the polymer rubber may be inferior.
The resulting modified polymer rubber may be used as a composition in combination with components such as other rubbers and additives.
上記他のゴムとして、乳化重合法で得られるスチレン−ブタジエン共重合体ゴム；アニオン重合触媒やＺｉｅｇｌｅｒ型触媒のような触媒を用いる溶液重合法で得られる、ポリブタジエンゴム、ブタジエン−イソプレンゴム共重合体ゴム、および、スチレン−ブタジエン共重合体ゴム；天然ゴム；ならびに、これらゴムの少なくとも２種の組合せ、を例示することができる。 As the other rubber, a styrene-butadiene copolymer rubber obtained by an emulsion polymerization method; a polybutadiene rubber, a butadiene-isoprene rubber copolymer obtained by a solution polymerization method using a catalyst such as an anionic polymerization catalyst or a Ziegler type catalyst. Examples include rubber and styrene-butadiene copolymer rubber; natural rubber; and combinations of at least two of these rubbers.
他のゴムと変性重合体ゴムとからなるゴム組成物中の後者の割合は、両者の合計量を１００重量％として、好ましくは１０重量％以上、より好ましくは２０重量％以上である。該割合が１０重量％未満であると、得られるゴム組成物の反撥弾性が改良され難く、加工性も良くない。 The ratio of the latter in the rubber composition comprising the other rubber and the modified polymer rubber is preferably 10% by weight or more, more preferably 20% by weight or more, with the total amount of both being 100% by weight. When the proportion is less than 10% by weight, the rebound resilience of the resulting rubber composition is difficult to improve and the processability is not good.
上記添加剤の種類や添加量は、得られるゴム組成物の使用目的に応じて決めればよい。添加剤として、ゴム工業で常用されている、硫黄のような加硫剤；ステアリン酸；亜鉛華；チアゾール系加硫促進剤、チウラム系加硫促進剤およびスルフェンアミド系加硫促進剤のような加硫促進剤；有機過酸化物；ＨＡＦ及びＩＳＡＦのようなグレードのカーボンブラックの如き補強剤；シリカ；炭酸カルシウム及びタルクのような充填剤；伸展油；加工助剤；並びに、老化防止剤、を例示することができる。カーボンブラックやシリカの添加量は、変性重合体ゴム、または、変性重合体ゴムと他のゴムとの合計量１００重量部に対して、好ましくは１０〜１５０重量部である。該添加量が１０重量部未満であると、ゴム成分に対する補強効果が不十分であり、１５０重量部を越えると、得られる組成物の伸びが低下することがある。 What is necessary is just to determine the kind and addition amount of the said additive according to the intended purpose of the rubber composition obtained. Sulfuric acid; zinc white; thiazole vulcanization accelerator, thiuram vulcanization accelerator and sulfenamide vulcanization accelerator commonly used in the rubber industry as additives Vulcanization accelerators; organic peroxides; reinforcing agents such as carbon black of grades such as HAF and ISAF; silica; fillers such as calcium carbonate and talc; extension oils; processing aids; Can be exemplified. The amount of carbon black or silica added is preferably 10 to 150 parts by weight with respect to 100 parts by weight of the modified polymer rubber or the total amount of the modified polymer rubber and other rubbers. When the addition amount is less than 10 parts by weight, the reinforcing effect on the rubber component is insufficient, and when it exceeds 150 parts by weight, the elongation of the resulting composition may be lowered.
上記ゴム組成物の製造方法は制限されない。該製造方法として、各成分をロールやバンバリーのような公知の混合機で混練する方法を例示することができる。得られるゴム組成物は通常加硫され、加硫されたゴム組成物として使用される。
本発明の製造方法によって得られる変性重合体ゴムは反撥弾性および加工性に優れているので、該ゴムからなるゴム組成物は、省燃費性に優れた自動車タイヤ用ゴムとして最適である。該ゴム組成物はまた、靴底用、床剤用および防振ゴム用のような用途として使用することができる。
The method for producing the rubber composition is not limited. Examples of the production method include a method of kneading each component with a known mixer such as a roll or Banbury. The resulting rubber composition is usually vulcanized and used as a vulcanized rubber composition.
Since the modified polymer rubber obtained by the production method of the present invention is excellent in rebound resilience and processability, the rubber composition comprising the rubber is optimal as a rubber for automobile tires excellent in fuel economy. The rubber composition can also be used for applications such as for shoe soles, flooring, and anti-vibration rubber.
以下、実施例によって本発明を説明するが、本発明はこれら実施例に限定されない。
実施例１
内容積２０リットルのステンレス製重合反応機を洗浄、乾燥し、乾燥窒素で置換した後、これに１，３−ブタジエン１４０４ｇ、スチレン３９６ｇ、テトラヒドロフラン １２２ｇ、ヘキサン１０．２ｋｇ、および、ｎ−ブチルリチウム（ｎ−ヘキサン溶液）１１．０ｍｍｏｌを添加し、攪拌下に６５℃で３時間重合し、重合混合物を得た。
重合混合物に[３−（ジエチルアミノ）プロピル]トリメトキシシラン１１．０ｍｍｏｌを添加し、攪拌下に６０分間反応させた後、メタノール１０ｍｌを加えて、更に５分間攪拌し、反応混合物を得た。
反応混合物を取り出し、これに２，６−ジ−ｔ−ブチル−ｐ−クレゾール（住友化学製、商品名スミライザーＢＨＴ）１０ｇを加え、ヘキサンの大部分を蒸発させた後、５５℃で１２時間減圧乾燥し、変性重合体ゴムを得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
Example 1
A stainless steel polymerization reactor having an internal volume of 20 liters was washed, dried, and replaced with dry nitrogen. 1-1.0 mmol of n-hexane solution) was added and polymerized at 65 ° C. for 3 hours with stirring to obtain a polymerization mixture.
After adding 11.0 mmol of [3- (diethylamino) propyl] trimethoxysilane to the polymerization mixture and reacting for 60 minutes with stirring, 10 ml of methanol was added and further stirring for 5 minutes to obtain a reaction mixture.
The reaction mixture was taken out, 10 g of 2,6-di-t-butyl-p-cresol (manufactured by Sumitomo Chemical Co., Ltd., trade name Smither BHT) was added, and most of the hexane was evaporated, followed by reducing the pressure at 55 ° C. for 12 hours. Drying gave a modified polymer rubber.
比較例１
ｎ−ブチルリチウム（ｎ−ヘキサン溶液）の添加量を８．９１ｍｍｏｌに変更したこと、四塩化スズ（カップリング剤）を０．４５ｍｍｏｌ添加したこと、及び[３−（ジエチルアミノ）プロピル]トリメトキシシランを添加しなかったこと以外、実施例１と同じに行い、重合体ゴムを得た。
Comparative Example 1
The addition amount of n-butyllithium (n-hexane solution) was changed to 8.91 mmol, 0.45 mmol of tin tetrachloride (coupling agent) was added, and [3- (diethylamino) propyl] trimethoxysilane A polymer rubber was obtained in the same manner as in Example 1 except that was not added.
比較例２
ｎ−ブチルリチウム（ｎ−ヘキサン溶液）の添加量を１０．０ｍｍｏｌに変更したこと、 変性剤及び添加量を[３−（ジエチルアミノ）プロピル]トリメトキシシラン１１．０ｍｍｏｌから[３−（ジメチルアミノ）プロピル]ジエトキシメチルシラン１０．０ｍｍｏｌに変更したこと以外、実施例１と同じに行い、重合体ゴムを得た。
Comparative Example 2
The addition amount of n-butyllithium (n-hexane solution) was changed to 10.0 mmol, and the modifier and addition amount were changed from 11.0 mmol of [3- (diethylamino) propyl] trimethoxysilane to [3- (dimethylamino) Polymer rubber was obtained in the same manner as in Example 1 except that the amount was changed to 10.0 mmol of propyl] diethoxymethylsilane.
実施例１で得た変性重合体ゴム、比較例１および２で得た重合体ゴムについて以下の測定を行い、結果を表２にまとめた。
１．ムーニー粘度
ＪＩＳ Ｋ−６３００に準拠して１００℃にて測定した。
２．ビニル含量
赤外分光分析法により測定した。
３．スチレン単位の含量
屈折率法により測定した。
４．カップリング率
ゲルパーミエイションクロマトグラフィーにより、測定曲線における高分子量分の面積と、低分子量分の面積との面積比から求めた。
５．加硫ゴムの反撥弾性
変性重合体ゴムまたは重合体ゴム表１に示す成分とをラボプラストミルにて混練した後、混練物を６インチロールで成形してシートを得た。該シートを１６０℃で４５分加熱して加硫させた後、加硫されたシートの６０℃での反撥弾性をリュプケレジリエンステスターで測定した。
The modified polymer rubber obtained in Example 1 and the polymer rubber obtained in Comparative Examples 1 and 2 were subjected to the following measurements, and the results are summarized in Table 2.
1. Mooney viscosity Measured at 100 ° C. according to JIS K-6300.
2. Vinyl content Measured by infrared spectroscopy.
3. Styrene unit content Measured by the refractive index method.
4). Coupling rate It calculated | required from the area ratio of the area for the high molecular weight in a measurement curve, and the area for a low molecular weight by the gel permeation chromatography.
5). Rebound resilience of vulcanized rubber The modified polymer rubber or polymer rubber was kneaded with a lab plast mill, and the kneaded product was molded with a 6-inch roll to obtain a sheet. The sheet was vulcanized by heating at 160 ° C. for 45 minutes, and then the rebound resilience at 60 ° C. of the vulcanized sheet was measured with a Lupke Resilience Tester.
＊１：ウルトラシルＶＮ３−Ｇ（デグッサ社製）
＊２：Ｓｉ６９（デグッサ社製）
＊３：Ｘ−１４０（共同石油社製アロマ油）
＊４：アンチゲン３Ｃ（住友化学社製 老化防止剤）
＊５：ソクシノールＣＺ（住友化学社製 加硫促進剤）
＊６：ソクシノールＤ（住友化学社製 加硫促進剤）
＊７：サンノックＮ（大内新興化学工業株式会社製）
* 1: Ultrasil VN3-G (Degussa)
* 2: Si69 (Degussa)
* 3: X-140 (Aroma oil manufactured by Kyodo Oil Co., Ltd.)
* 4: Antigen 3C (Anti-aging agent manufactured by Sumitomo Chemical Co., Ltd.)
* 5: Soccinol CZ (vulcanization accelerator manufactured by Sumitomo Chemical Co., Ltd.)
* 6: Soxinol D (vulcanization accelerator manufactured by Sumitomo Chemical Co., Ltd.)
* 7: Sunnock N (Ouchi Shinsei Chemical Co., Ltd.)
＊１ 変性化合物
Ａ：[３−（ジエチルアミノ）プロピル]トリメトキシシラン
Ｂ：[３−（ジメチルアミノ）プロピル]ジエトキシメチルシラン
* 1 Modified compound A: [3- (Diethylamino) propyl] trimethoxysilane B: [3- (Dimethylamino) propyl] diethoxymethylsilane
Claims (4)
工程１：アルカリ金属触媒の存在下、炭化水素溶媒中で、共役ジエンモノマー、又は、共役ジエンモノマーと芳香族ビニルモノマーとを重合させ、アルカリ金属末端を有する活性重合体を得る工程、
工程２：該活性重合体と、下式（１）（式中、Ｒ1、Ｒ2およびＲ3はそれぞれ独立の炭素数１〜４のアルキル基を表し、Ｒ4およびＲ5はそれぞれ独立の炭素数１〜６のアルキル基を表し、ｎは０または１〜１０の整数を表す）で表される化合物とを反応させて、変性重合体ゴムを得る工程。
Step 1: A step of polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of an alkali metal catalyst to obtain an active polymer having an alkali metal terminal,
Step 2: The active polymer and the following formula (1) (wherein R 1 , R 2 and R 3 each independently represent an alkyl group having 1 to 4 carbon atoms, and R 4 and R 5 are each independently A step of obtaining a modified polymer rubber by reacting with a compound represented by an alkyl group having 1 to 6 carbon atoms, wherein n represents 0 or an integer of 1 to 10.
A rubber composition comprising the modified polymer rubber according to claim 1 in an amount of 10% by weight or more in the rubber component.
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