JP4655706B2 - Modified diene polymer rubber and process for producing the same - Google Patents
Modified diene polymer rubber and process for producing the same Download PDFInfo
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本発明は、優れた反撥弾性を有する両末端変性重合体ゴム及びその製造方法に関するものである。この製造方法で得られる両末端変性重合体ゴムは、優れた省燃費性を有する自動車タイヤに最適である。 The present invention relates to a both-end-modified polymer rubber having excellent rebound resilience and a method for producing the same. The both-end modified polymer rubber obtained by this production method is optimal for automobile tires having excellent fuel economy.
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。 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.
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。 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.
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。 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。 Further, 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.
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という問題があった。 However, in recent years, the demand for fuel economy of automobile tires has become more advanced against the background of environmental considerations, and there has been a problem that the above copolymer rubber cannot sufficiently meet this demand. .
かかる状況において、本発明が解決しようとする課題は、優れた反撥弾性を有する両末端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。 Under such circumstances, the problem to be solved by the present invention is to provide a both-end modified polymer rubber having excellent rebound resilience and a method for producing the same.
すなわち本発明のうち第一の発明は、以下の工程から得られる、両末端が変性されたジエン系重合体ゴムに係るものである。
工程１：下式（１）で表される化合物の存在下に、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て、アルカリ金属末端を有する活性重合体を製造する工程
工程２：該活性重合体と、下式（２）で表される化合物を反応させて、両末端が変性された変性重合体ゴムを製造する工程
（式（１）中、Ｒ1はＮ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ，Ｎ−ジプロピルアミノ基、Ｎ，Ｎ−ジブチルアミノ基、モルホリノ基またはイミダゾリル基を表し、Ｘは共役ジエンモノマー又は芳香族ビニルモノマーｍユニットの重合からなる飽和又は不飽和炭化水素を表し、ｍは０〜１０の整数を表し、ｎは１〜１０の整数を表し、Ｍはアルカリ金属を表す。）
（式（２）中、Ｒ2は炭素数１〜４のアルキル基を表し、Ｒ3及びＲ4はそれぞれ独立の炭素数が１〜４のアルキル基又はアルコキシ基を表し、Ｒ5及びＲ6はそれぞれ独立の炭素数が１〜６のアルキル基を表し、ｐは０または１〜１０の整数を表す。）
本発明のうち第二の発明は、上記の工程による両末端変性重合体ゴムの製造方法に係るものである。
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。
That is, the first invention of the present invention relates to a diene polymer rubber having both ends modified, obtained from the following steps.
Step 1: A step of producing an active polymer having an alkali metal terminal by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a compound represented by the following formula (1): Step 2 : A step of reacting the active polymer with a compound represented by the following formula (2) to produce a modified polymer rubber having both ends modified
(In the formula (1), R 1 represents an N, N-dimethylamino group, an N, N-diethylamino group, an N, N-dipropylamino group, an N, N-dibutylamino group, a morpholino group or an imidazolyl group , X represents a saturated or unsaturated hydrocarbon formed by polymerization of m units of a conjugated diene monomer or an aromatic vinyl monomer, m represents an integer of 0 to 10, n represents an integer of 1 to 10, and M represents an alkali metal. To express.)
(In formula (2), R 2 represents an alkyl group having 1 to 4 carbon atoms, R 3 and R 4 each represents an independent alkyl group or alkoxy group having 1 to 4 carbon atoms, and R 5 and R 6. Each represents an independent alkyl group having 1 to 6 carbon atoms, and p represents 0 or an integer of 1 to 10.)
The second invention of the present invention relates to a method for producing a both-end-modified polymer rubber by the above-described steps.
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、１，３−ヘキサジエン等を例示することができる。これらの中でも、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、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, 1,3-hexadiene, and the like. Can do. Among these, 1,3-butadiene and isoprene are 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等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.
式（１）中、Ｒ 1 はＮ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ，Ｎ−ジプロピルアミノ基、Ｎ，Ｎ−ジブチルアミノ基、モルホリノ基、イミダゾリル基である。
In formula (1), R 1 is a N, N-dimethylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, a morpholino group, imidazolinium Le group .
式（１）中、Ｘは共役ジエンモノマー又は芳香族ビニルモノマーｍユニットの重合からなる飽和又は不飽和炭化水素を表し、ｍは０以上１０以下の整数を表すが、ｍは０以上５以下の整数が好ましい。ｍが０の場合、溶液中での会合が強く、炭化水素溶媒への溶解性が悪化するため重合速度が遅くなることもある。ｍが５以上の場合、分子量が大きくなるため、使用量が増大するため好ましくない。特に炭化水素溶媒への溶解性に優れ、安定に取り扱えるイソプレンモノマー２ユニットの重合体からなる不飽和炭化水素の場合が好ましい。 In the formula (1), X represents a saturated or unsaturated hydrocarbon formed by polymerization of a conjugated diene monomer or an aromatic vinyl monomer m unit, m represents an integer of 0 or more and 10 or less, and m is 0 or more and 5 or less. An integer is preferred. When m is 0, the association in the solution is strong and the solubility in the hydrocarbon solvent is deteriorated, so that the polymerization rate may be slow. When m is 5 or more, the molecular weight increases, and the amount used is increased, which is not preferable. Particularly preferred is an unsaturated hydrocarbon comprising a polymer of 2 units of isoprene monomer which is excellent in solubility in a hydrocarbon solvent and can be handled stably.
式（１）中、ｎは１以上１０以下の整数であるが、３以上１０以下の整数が好ましい。３以下の場合、該化合物の反応性が高いため、合成が難しく、また重合も制御しにくい。 In formula (1), n is an integer of 1 to 10, but an integer of 3 to 10 is preferable. In the case of 3 or less, since the reactivity of the compound is high, synthesis is difficult and polymerization is difficult to control.
式（１）中、Ｍはアルカリ金属を表し、Ｌｉ、Ｎａ、Ｋ、Ｃｓ等を例示することができるが、炭化水素溶媒への溶解性が高いＬｉが好ましい。 In the formula (1), M represents an alkali metal, and examples thereof include Li, Na, K, Cs, etc., but Li having high solubility in a hydrocarbon solvent is preferable.
式（１）で表される化合物としては、３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウム、３−（Ｎ，Ｎ−ジエチルアミノ）−１−プロピルリチウム、３−（Ｎ，Ｎ−ジプロピルアミノ）−１−プロピルリチウム、３−（Ｎ，Ｎ−ジブチルアミノ）−１−プロピルリチウム、３−モルホリノ−１−プロピルリチウム、３−イミダゾリル−１−プロピルリチウム、及びこれらをブタジエン、イソプレン、又はスチレン１〜１０ユニットにより鎖延長した化合物等があげられるが、分子量分布の狭い活性重合体が迅速な反応で得られ、また得られる重合体は省燃費性を著しく改良できるという観点から３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウム及び３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素が好ましい。さらに工業的には炭化水素溶媒への溶解性に優れる、３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素が好ましい。 Examples of the compound represented by the formula (1) include 3- (N, N-dimethylamino) -1-propyllithium, 3- (N, N-diethylamino) -1-propyllithium, 3- (N, N- dipropylamino) -1-propyl lithium, 3- (N, N-dibutylamino) -1-propyl lithium, 3-morpholino-1-propyl lithium, 3- imidazolinium-1-propyl lithium, and these butadiene , Isoprene, or compounds extended in chain by 1 to 10 units of styrene, and the like. An active polymer having a narrow molecular weight distribution can be obtained by a rapid reaction, and the resulting polymer can significantly improve fuel economy. To 3- (N, N-dimethylamino) -1-propyllithium and 3- (N, N-dimethylamino) -1-propyllithium Over hydrocarbon it is preferred that the two units are polymerized. Further, industrially preferred is an activated hydrocarbon obtained by polymerizing 2-unit isoprene monomer with 3- (N, N-dimethylamino) -1-propyllithium, which is excellent in solubility in a hydrocarbon solvent.
本発明における工程１で共役ジエンモノマーと芳香族ビニルモノマーとの組合わせを用いる場合、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、得られる活性重合体が炭化水素溶媒に不溶となり、その結果、均一な重合が不可能となる場合がある。該比が９０／１０を越えると、得られる活性重合体の強度が低下する場合がある。 When a combination of a conjugated diene monomer and an aromatic vinyl monomer is used in Step 1 of the present invention, the weight ratio of the conjugated diene monomer / aromatic vinyl monomer is preferably 50/50 to 90/10, and 55/45 to 85 / 15 is more preferable. When the ratio is less than 50/50, the resulting active polymer becomes insoluble in the hydrocarbon solvent, and as a result, uniform polymerization may not be possible. If the ratio exceeds 90/10, the strength of the resulting active polymer may be reduced.
工程１における重合方法は特に制限されず、公知の方法であってもよい。該工程においては、炭化水素溶媒；ランダマイザー；および、得られる活性重合体中のビニル結合（共役ジエンモノマーに由来する）の含有量を調節するための添加剤、のような通常使用されている公知の溶媒や添加剤を用いてもよい。 The polymerization method in Step 1 is not particularly limited, and may be a known method. In the process, hydrocarbon solvents; randomizers; and additives for adjusting the content of vinyl bonds (derived from conjugated diene monomers) in the resulting active polymer are commonly used. Known solvents and additives may be used.
上記の、炭化水素溶媒は、式（１）で表される化合物を失活させない溶媒である。適した溶媒として、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、及びエチルベンゼン、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 is a solvent that does not deactivate the compound represented by the formula (1). Suitable solvents can 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.
上記の、ビニル結合の含有量を調節するための添加剤として、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 additive for adjusting the vinyl bond content include a Lewis basic compound. 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、及び１，４−ジオキサンのような環状エーテル；ジエチルエーテル及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、及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及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。 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 Examples include ethers and aliphatic diethers such as diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole.
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、及びキノリンなどを例示することができる。 Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-diethylaniline, pyridine, and quinoline.
式（２）中、好ましいＲ2はメチル基、又はエチル基である。Ｒ3及びＲ4は同じであっても異なってもよく、好ましいＲ3及びＲ4はメチル基、エチル基、メトキシ基、又はエトキシ基である。 In formula (2), preferred R 2 is a methyl group or an ethyl group. R 3 and R 4 may be the same or different, and preferred R 3 and R 4 are a methyl group, an ethyl group, a methoxy group, or an ethoxy group.
式（２）中、Ｒ5及びＲ6は同じであっても異なってもよく、好ましいＲ5及びＲ6はメチル基、又はエチル基である。 In formula (2), R 5 and R 6 may be the same or different, and preferred R 5 and R 6 are a methyl group or an ethyl group.
式（２）中、好ましいｐは３又は４である。ｐが２以下のものは、ｐ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い。さらにｐが１及び２のものは製造上、合成が難しい。またｐが５以上の場合には、（２）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 (2), preferable p is 3 or 4. When p is 2 or less, the resulting fuel composition has low fuel efficiency compared to when p is 3 or 4. Further, those having p of 1 and 2 are difficult to synthesize in production. On the other hand, when p is 5 or more, the molecular weight of (2) becomes large, so that distillation purification becomes difficult in the production process.
式（２）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、[３−（ジメチルアミノ）プロピル]メチルジメトキシシラン、[３−（ジエチルアミノ）プロピル]メチルジメトキシシラン、[３−（ジメチルアミノ）プロピル]エチルジメトキシシラン、[３−（ジエチルアミノ）プロピル]エチルジメトキシシラン、[３−（ジメチルアミノ）プロピル]ジメチルメトキシシラン、[３−（ジメチルアミノ）プロピル]ジエチルメトキシシラン、[３−（ジエチルアミノ）プロピル]ジメチルメトキシシラン、[３−（ジエチルアミノ）プロピル]ジエチルメトキシシラン、 [（３−メチル−３−エチルアミノ）プロピル]メチルジメトキシシラン、[（３−メチル−３−エチルアミノ）プロピル]エチルジメトキシシラン、[３−（ジメチルアミノ）プロピル]メチルジエトキシシラン、[３−（ジエチルアミノ）プロピル]メチルジエトキシシラン、[３−（ジメチルアミノ）プロピル]エチルジエトキシシラン、[３−（ジエチルアミノ）プロピル]エチルジエトキシシラン、[３−（ジメチルアミノ）プロピル]ジメチルエトキシシラン、[３−（ジメチルアミノ）プロピル]ジエチルエトキシシラン、[３−（ジエチルアミノ）プロピル]ジメチルエトキシシラン、[３−（ジエチルアミノ）プロピル]ジエチルエトキシシラン、 [（３−メチル−３−エチルアミノ）プロピル]メチルジエトキシシラン、[（３−メチル−３−エチルアミノ）プロピル]エチルジエトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝トリメトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝トリエトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝トリメトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝トリエトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝メチルジメトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝メチルジエトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝メチルジメトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝メチルジエトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝ジメチルメトキシシラン、｛３−[ジ（トリメチルシリル）アミノ]プロピル｝ジメチルエトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝ジメチルメトキシシラン、｛３−[ジ（ｔ−ブチルジメチルシリル）アミノ]プロピル｝ジメチル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、[３−（ジエチルアミノ）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]メチルジメトキシシラン、[３−（ジエチルアミノ）プロピル]ジメチルメトキシシランが好ましい。 Examples of the compound represented by the formula (2) include [3- (dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [(3-methyl-3-ethylamino) propyl] trimethoxysilane, [(3-methyl-3-ethylamino) propyl] triethoxysilane, [3- ( Dimethylamino) propyl] methyldimethoxysilane, [3- (diethylamino) propyl] methyldimethoxysilane, [3- (dimethylamino) propyl] ethyldimethoxysilane, [3- (diethylamino) propyl] ethyldimethoxysilane, [3- ( Dimethylamino) propyl] dimethylmethoxysilane, [3- (dimethylamino) pro Ru] diethylmethoxysilane, [3- (diethylamino) propyl] dimethylmethoxysilane, [3- (diethylamino) propyl] diethylmethoxysilane, [(3-methyl-3-ethylamino) propyl] methyldimethoxysilane, [(3 -Methyl-3-ethylamino) propyl] ethyldimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [3- (diethylamino) propyl] methyldiethoxysilane, [3- (dimethylamino) propyl] Ethyldiethoxysilane, [3- (diethylamino) propyl] ethyldiethoxysilane, [3- (dimethylamino) propyl] dimethylethoxysilane, [3- (dimethylamino) propyl] diethylethoxysilane, [3- (diethylamino) Propyl] dimethylethoxysilane, [3- (di Tilamino) propyl] diethylethoxysilane, [(3-methyl-3-ethylamino) propyl] methyldiethoxysilane, [(3-methyl-3-ethylamino) propyl] ethyldiethoxysilane, {3- [di ( Trimethylsilyl) amino] propyl} trimethoxysilane, {3- [di (trimethylsilyl) amino] propyl} triethoxysilane, {3- [di (t-butyldimethylsilyl) amino] propyl} trimethoxysilane, {3- [ Di (t-butyldimethylsilyl) amino] propyl} triethoxysilane, {3- [di (trimethylsilyl) amino] propyl} methyldimethoxysilane, {3- [di (trimethylsilyl) amino] propyl} methyldiethoxysilane, { 3- [Di (t-butyldimethylsilyl) amino] propyl} methyldimethoxy {3- [di (t-butyldimethylsilyl) amino] propyl} methyldiethoxysilane, {3- [di (trimethylsilyl) amino] propyl} dimethylmethoxysilane, {3- [di (trimethylsilyl) amino] propyl } Dimethylethoxysilane, {3- [di (t-butyldimethylsilyl) amino] propyl} dimethylmethoxysilane, {3- [di (t-butyldimethylsilyl) amino] propyl} dimethylethoxysilane, etc. it can. Among these, [3- (diethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] methyldimethoxysilane, [ 3- (Diethylamino) propyl] dimethylmethoxysilane is preferred.
式（２）化合物の使用量は、活性重合体１モルあたり、通常０．１〜１０モルであり、好ましくは０．５〜２モルである。該使用量が０．１モル未満であると、省燃費性改良の効果が小さく、該使用量が１０モルを超えると、未反応のアミン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、該溶媒中のアミン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 a compound of Formula (2) is 0.1-10 mol normally with respect to 1 mol of active polymers, Preferably it is 0.5-2 mol. If the amount used is less than 0.1 mol, the effect of improving fuel economy is small, and if the amount used exceeds 10 mol, unreacted amine compound remains in the solvent, which is economically undesirable. . This is because, when the solvent is recycled and reused, a step of separating the amine compound in the solvent is necessary.
工程２の反応は迅速に進行する。該反応の温度や時間は制限されず、それぞれ一般に、室温〜８０℃、数秒〜数時間である。式（１）化合物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 in step 2 proceeds rapidly. The temperature and time of the reaction are not limited and are generally room temperature to 80 ° C. and several seconds to several hours, respectively. As a preferred contact method between the compound of formula (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.
変性重合体ゴムの混練加工性の観点から、工程２の前又は後に、活性重合体に対して下式（式中Ｒ'はアルキル基、アルコキシ基、アリル基、アルケニル基、シクロアルケニル基又は芳香族炭化水素基、Ｍ'はケイ素又はスズ原子、Ｙはハロゲン原子、ｂは０〜２の整数、ｃは２〜４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。
Ｒ'ｂＭ'Ｙｃ
From the viewpoint of kneading processability of the modified polymer rubber, before or after step 2, the active polymer is represented by the following formula (wherein R ′ is an alkyl group, alkoxy group, allyl group, alkenyl group, cycloalkenyl group or aromatic A coupling agent represented by a group hydrocarbon group, M ′ is a silicon or tin atom, Y is a halogen atom, b is an integer of 0 to 2, and c is an integer of 2 to 4) may be added.
R'bM'Yc
上記カップリング剤の添加量は、活性重合体１モル当たり、通常０．００５〜０．４モルであり、好ましくは０．０１〜０．３モルである。該添加量が０．００５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０．３モルを超えると、アミン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。また溶液の粘性が非常に高くなることがある。 The amount of the coupling agent added is usually 0.005 to 0.4 mol, preferably 0.01 to 0.3 mol, per mol of the active polymer. When the added amount is less than 0.005 mol, the effect of improving the processability of the modified polymer rubber is small. When the added amount exceeds 0.3 mol, the ratio of the active polymer that reacts with the amine compound is reduced, so that the effect of improving fuel economy is reduced. Also, the viscosity of the solution can be very high.
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、又は、（２）スチームを添加する方法のような凝固法によって、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 simple coagulation 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。 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.
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用いてもよい。 The resulting modified polymer rubber may be used 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、及び、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、加工性も良くならない。 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 improved.
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等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。 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. As additives, vulcanizing agents commonly used in the rubber industry, such as sulfur; stearic acid; zinc white; thiazole vulcanization accelerator, thiuram vulcanization accelerator and sulfenamide vulcanization accelerator Organic peroxides; reinforcing agents such as carbon black grades such as HAF and ISAF; silica; fillers such as calcium carbonate and talc; extension oils; processing aids; and anti-aging The agent can be exemplified.
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。 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.
本発明の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。 Since the modified polymer rubber 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・乾燥した後、反応機を乾燥窒素で置換した。次いで、これに３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素（ＦＭＣ社製、ＡＩ−２００ＣＥ、シクロヘキサン溶液）１１．３ｍｍｏｌと、１，３−ブタジエン１５２０ｇと、スチレン４８０ｇと、テトラヒドロフラン３２４ｇと、ヘキサン１０．２ｋｇとを仕込み、攪拌下に６５℃で３時間重合させた。得られた重合反応混合物に [３−（ジエチルアミノ）プロピル]トリメトキシシラン（式（２）化合物）１１．３ｍｍｏｌを添加し、攪拌下に６５℃でさらに３０分間反応させた。得られた反応混合物にメタノール１０ｍｌを加えて、６５℃でさらに５分間攪拌した。得られた反応混合物を取り出し、これに１０ｇの２，６−ジ−ｔ−ブチル−ｐ−クレゾール（住友化学製のスミライザーＢＨＴ：以下同様）を加えた後、ヘキサンの大部分を蒸発させ、次いで、５５℃で１２時間減圧乾燥し、両末端が変性された重合体ゴムを得た。
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
Example 1
After washing and drying a stainless polymerization reactor having an internal volume of 20 liters, the reactor was replaced with dry nitrogen. Next, 11.3 mmol of activated hydrocarbon (FMC, AI-200CE, cyclohexane solution) obtained by polymerizing 2 units of isoprene monomer to 3- (N, N-dimethylamino) -1-propyllithium, 1520 g of 3-butadiene, 480 g of styrene, 324 g of tetrahydrofuran and 10.2 kg of hexane were charged and polymerized at 65 ° C. for 3 hours with stirring. 11.3-mmol of [3- (diethylamino) propyl] trimethoxysilane (formula (2) compound) was added to the resulting polymerization reaction mixture, and the mixture was further reacted at 65 ° C. for 30 minutes with stirring. 10 ml of methanol was added to the obtained reaction mixture, and the mixture was further stirred at 65 ° C. for 5 minutes. The obtained reaction mixture was taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical's BHT: the same applies hereinafter) was added thereto, and most of the hexane was evaporated. And dried under reduced pressure at 55 ° C. for 12 hours to obtain a polymer rubber modified at both ends.
実施例２
１，３−ブタジエン１５６０ｇと、スチレン４４０ｇを用いたこと、及び３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素（ＦＭＣ社製、ＡＩ−２００ＣＥ、シクロヘキサン溶液）の添加量を１１．７ｍｍｏｌに変更したこと、及び、[３−（ジエチルアミノ）プロピル]トリメトキシシランの代わりに[３−（ジメチルアミノ）プロピル]ジエトキシメチルシラン１１．７ｍｍｏｌを用いたこと以外、実施例１と同じに行い、両末端が変性された重合体ゴムを得た。
Example 2
1,560 g of 1,3-butadiene and 440 g of styrene, and an activated hydrocarbon obtained by polymerizing 2 units of isoprene monomer on 3- (N, N-dimethylamino) -1-propyllithium (manufactured by FMC, AI- 200CE, cyclohexane solution) was added to 11.7 mmol, and [3- (dimethylamino) propyl] diethoxymethylsilane 11.7 mmol was used instead of [3- (diethylamino) propyl] trimethoxysilane. Except that it was used, the same procedure as in Example 1 was carried out to obtain a polymer rubber modified at both ends.
比較例１
３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素（ＦＭＣ社製、ＡＩ−２００ＣＥ、シクロヘキサン溶液）１１．３ｍｍｏｌをｎ−ブチルリチウム（ｎ−ヘキサン溶液）１１．３ｍｍｏｌに変更したこと以外、実施例１と同じに行い、変性重合体ゴムを得た。
Comparative Example 1
11.3 mmol of activated hydrocarbon (FMC, AI-200CE, cyclohexane solution) obtained by polymerizing 2 units of isoprene monomer on 3- (N, N-dimethylamino) -1-propyllithium was added to n-butyllithium (n- (Hexane solution) A modified polymer rubber was obtained in the same manner as in Example 1 except that it was changed to 11.3 mmol.
比較例２
３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素（ＦＭＣ社製、ＡＩ−２００ＣＥ、シクロヘキサン溶液）１１．３ｍｍｏｌをｎ−ブチルリチウム（ｎ−ヘキサン溶液）１１．３ｍｍｏｌに変更したこと以外、実施例２と同じに行い、重合体ゴムを得た。
Comparative Example 2
11.3 mmol of activated hydrocarbon (FMC, AI-200CE, cyclohexane solution) obtained by polymerizing 2 units of isoprene monomer on 3- (N, N-dimethylamino) -1-propyllithium was added to n-butyllithium (n- (Hexane solution) A polymer rubber was obtained in the same manner as in Example 2 except that the content was changed to 11.3 mmol.
比較例３
１，３−ブタジエン１４０４ｇと、スチレン３９６ｇを用いたことｎ−ブチルリチウム（ｎ−ヘキサン溶液）の添加量を８．７０ｍｍｏｌに変更したこと、四塩化スズ（カップリング剤）を０．１７ｍｍｏｌ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、比較例１と同じに行い、重合体ゴムを得た。
Comparative Example 3
Using 1,4-butadiene 1404 g and styrene 396 g, changing the addition amount of n-butyllithium (n-hexane solution) to 8.70 mmol, adding 0.17 mmol of tin tetrachloride (coupling agent) This was performed in the same manner as in Comparative Example 1 except that [3- (diethylamino) propyl] trimethoxysilane was not added to obtain a polymer rubber.
＊１ 式（１）で表される化合物
Ｉ：３−（Ｎ，Ｎ−ジメチルアミノ）−１−プロピルリチウムにイソプレンモノマー２ユニットを重合させた活性炭化水素（ＦＭＣ社製、ＡＩ−２００ＣＥ、シクロヘキサン溶液を使用）
＊２ 変性剤
II：[３−（ジエチルアミノ）プロピル]トリメトキシシラン
III：[３−（ジメチルアミノ）プロピル]ジエトキシメチルシラン
* 1 Compound I represented by formula (1) I: Active hydrocarbon obtained by polymerizing 2 units of isoprene monomer on 3- (N, N-dimethylamino) -1-propyllithium (manufactured by FMC, AI-200CE, cyclohexane Use solution)
* 2 Denaturant
II: [3- (Diethylamino) propyl] trimethoxysilane
III: [3- (Dimethylamino) propyl] diethoxymethylsilane
Claims (8)
工程１：下式（１）で表される化合物の存在下に、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て、アルカリ金属末端を有する活性重合体を製造する工程
工程２：該活性重合体と、下式（２）で表される化合物を反応させて、両末端が変性された変性重合体ゴムを製造する工程
（式（１）中、Ｒ1はＮ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ，Ｎ
−ジプロピルアミノ基、Ｎ，Ｎ−ジブチルアミノ基、モルホリノ基またはイミダゾリル基を表し、Ｘは共役ジエンモノマー又は芳香族ビニルモノマーｍユニットの重合からなる飽和又は不飽和炭化水素を表し、ｍは０〜１０の整数を表し、ｎは１〜１０の整数を表し、Ｍはアルカリ金属を表す。）
（式（２）中、Ｒ2は炭素数１〜４のアルキル基を表し、Ｒ3及びＲ4はそれぞれ独立の炭素数が１〜４のアルキル基又はアルコキシ基を表し、Ｒ5及びＲ6はそれぞれ独立の炭素数が１〜６のアルキル基を表し、ｐは０または１〜１０の整数を表す。） A diene polymer rubber having both ends modified, obtained from the following steps.
Step 1: A step of producing an active polymer having an alkali metal terminal by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a compound represented by the following formula (1): Step 2 : A step of reacting the active polymer with a compound represented by the following formula (2) to produce a modified polymer rubber having both ends modified
(In the formula (1), R 1 is N, N-dimethylamino group, N, N-diethylamino group, N, N
-Represents a dipropylamino group, an N, N-dibutylamino group, a morpholino group or an imidazolyl group , X represents a saturated or unsaturated hydrocarbon consisting of polymerization of m units of a conjugated diene monomer or an aromatic vinyl monomer, and m is 0 Represents an integer of -10, n represents an integer of 1 to 10, and M represents an alkali metal. )
(In formula (2), R 2 represents an alkyl group having 1 to 4 carbon atoms, R 3 and R 4 each represents an independent alkyl group or alkoxy group having 1 to 4 carbon atoms, and R 5 and R 6. Each represents an independent alkyl group having 1 to 6 carbon atoms, and p represents 0 or an integer of 1 to 10.)
工程１：下式（１）で表される化合物の存在下に、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て、アルカリ金属末端を有する活性重合体を製造する工程
工程２：該活性重合体と、下式（２）で表される化合物を反応させて、両末端が変性された変性重合体ゴムを製造する工程
（式（１）中、Ｒ 1 はＮ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ，Ｎ
−ジプロピルアミノ基、Ｎ，Ｎ−ジブチルアミノ基、モルホリノ基またはイミダゾリル基を表わし、Ｘは共役ジエンモノマー又は芳香族ビニルモノマーｍユニットの重合からなる飽和又は不飽和炭化水素を表し、ｍは０〜１０の整数を表し、ｎは１〜１０の整数を表し、Ｍはアルカリ金属を表す。）
（式（２）中、Ｒ 2 は炭素数１〜４のアルキル基を表し、Ｒ 3 及びＲ 4 はそれぞれ独立の炭素数が１〜４のアルキル基又はアルコキシ基を表し、Ｒ 5 及びＲ 6 はそれぞれ独立の炭素数が１〜６のアルキル基を表し、ｐは０または１〜１０の整数を表す。） A method for producing a both-end-modified polymer rubber by the following steps.
Step 1: A step of producing an active polymer having an alkali metal terminal by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a compound represented by the following formula (1):
Step 2: A step of producing a modified polymer rubber having both ends modified by reacting the active polymer with a compound represented by the following formula (2):
(In the formula (1), R 1 is N, N-dimethylamino group, N, N-diethylamino group, N, N
-Represents a dipropylamino group, an N, N-dibutylamino group, a morpholino group or an imidazolyl group, X represents a saturated or unsaturated hydrocarbon consisting of polymerization of m units of a conjugated diene monomer or an aromatic vinyl monomer, and m represents 0 Represents an integer of -10, n represents an integer of 1 to 10, and M represents an alkali metal. )
(In formula (2), R 2 represents an alkyl group having 1 to 4 carbon atoms, R 3 and R 4 each represents an independent alkyl group or alkoxy group having 1 to 4 carbon atoms, and R 5 and R 6. Each represents an independent alkyl group having 1 to 6 carbon atoms, and p represents 0 or an integer of 1 to 10.)
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