JPS61168605A - Polymer of substituted 1,3-butadiene derivative and its production - Google Patents
Polymer of substituted 1,3-butadiene derivative and its productionInfo
- Publication number
- JPS61168605A JPS61168605A JP1030785A JP1030785A JPS61168605A JP S61168605 A JPS61168605 A JP S61168605A JP 1030785 A JP1030785 A JP 1030785A JP 1030785 A JP1030785 A JP 1030785A JP S61168605 A JPS61168605 A JP S61168605A
- Authority
- JP
- Japan
- Prior art keywords
- butadiene
- substituted
- polymer
- silyl
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、置換−１，３−ブタジエン誘導体を重合する
事によって得られる新規な重合体及びその製造方法に関
するものであり、詳しくは、反応性シリル基を有するジ
エン系重合体及びその製造方法に関するものである。Detailed Description of the Invention The present invention relates to a novel polymer obtained by polymerizing substituted-1,3-butadiene derivatives and a method for producing the same. This invention relates to polymers and methods for producing the same.
従来の反応性シラン化合物は、無機物の表面処理を目的
とする用途が多く、大多数は低分子の化合物が多かった
。又、反応性シリル基を有するビニール化合物やメタク
リル酸系化合物等の重合可能なシラン化合物もあるが、
これらは単独で重合される事は殆どなく、他のプラスチ
ックの改質の目的で少量共重合される程度であった。Conventional reactive silane compounds are often used for the purpose of surface treatment of inorganic materials, and most of them are low-molecular compounds. There are also polymerizable silane compounds such as vinyl compounds and methacrylic acid compounds that have reactive silyl groups.
These are rarely polymerized alone, and are only copolymerized in small amounts for the purpose of modifying other plastics.
本発明者等は、従来のシラン化合物にない反応性シリル
基とジエン構造を有する重合体が各種用途に展開可能な
事を知見し、本発明を完成したものである。The present inventors completed the present invention based on the knowledge that a polymer having a reactive silyl group and a diene structure, which are not found in conventional silane compounds, can be used for various purposes.
即ち、本発明の重合体は、反応性シリル基とジエン構造
を利用して、無機フィラー表面にゴム弾性を付加しプラ
スチックの耐衝撃性の改良、磁性体表面にゴム弾性を付
加する事による高配向性磁性体の製造、ゴムとのブレン
ド後の共加硫更には反応性シリル基を利用する架橋、無
機フィラー表面を処理する事によるＦＲＰ等の耐加水分
解性の改良、ガラス、セラミックス、ゴム製品の接着剤
及びカップリング剖等の用途に使用出来、その他各種の
用途展開が可能である。That is, the polymer of the present invention utilizes a reactive silyl group and a diene structure to improve the impact resistance of plastics by adding rubber elasticity to the surface of an inorganic filler, and to improve the impact resistance of plastics by adding rubber elasticity to the surface of a magnetic material. Production of oriented magnetic materials, co-vulcanization after blending with rubber, crosslinking using reactive silyl groups, improvement of hydrolysis resistance of FRP etc. by treating the surface of inorganic fillers, glass, ceramics, rubber It can be used as an adhesive for products, as a coupling agent, and can be used for a variety of other applications.
更に、場合によっては、置換−１，３−ブタジエン誘導
体モノマーを上記物質に添加後、加熱重合する事も出来
る。Furthermore, in some cases, a substituted 1,3-butadiene derivative monomer can be added to the above substance and then heated and polymerized.
又、従来のシランカップリング剤と同様な用途にも使用
出来る。It can also be used for the same purposes as conventional silane coupling agents.
本発明の反応性シリル基を有する新規なジエン系重合体
は、構造式〔１〕で表される置換−１，３−ブタジエン
誘導体を重合する事によって得られる。The novel diene polymer having a reactive silyl group of the present invention can be obtained by polymerizing a substituted-1,3-butadiene derivative represented by the structural formula [1].
（Ｘは、水素又は５ｔＲＩＲｔＲ１を示し、Ｘの１つは
必ずＳｉＲ，Ｒ１Ｒ１である。又、Ｒｌｓ Ｒｇ、Ｒ１
は、ハロゲン、低級アルコキシ基又は低級アルキル基を
示し、Ｒ＋、Ｒｚ、Ｒ３が同時に低級アルキル基である
場合を除（。）
本発明の置換−１，３−ブタジエン誘導体としては、１
−〔トリメトキシ〕シリルー１．３−ブタジエン、１−
〔メトキシジメチル〕シリル−１，３−ブタジエン、１
− （ジメトキシメチル〕シリル−１，３−ブタジエン
、ｌ−〔トリクロロ〕シリルー１．３−ブタジエン、１
−〔ジメチルクロロ〕シリルー１．３〜ブタジェン等が
挙げられる。(X represents hydrogen or 5tRIRtR1, and one of X is always SiR, R1R1. Also, Rls Rg, R1
represents a halogen, a lower alkoxy group, or a lower alkyl group, except when R+, Rz, and R3 are all lower alkyl groups (.) As the substituted-1,3-butadiene derivative of the present invention, 1
-[trimethoxy]silyl-1,3-butadiene, 1-
[Methoxydimethyl]silyl-1,3-butadiene, 1
- (dimethoxymethyl]silyl-1,3-butadiene, l-[trichloro]silyl-1,3-butadiene, 1
-[dimethylchloro]silyl-1.3 to butadiene and the like.
又、２−〔トリメトキシ〕シリルー１．３−ブタジエン
、２−〔メトキシジメチル〕シリル−１，３−ブタジエ
ン、２−〔ジメトキシメチル〕シリル−１，３−ブタジ
エン、２−〔トリクロロ〕シリルー１．３−ブタジエン
、２−〔ジメチルクロロ〕シリルー１．３−ブタジエン
等も挙げられる
本発明重合体の分子量には制限がなく、ポリマー及びオ
リゴマーの何れであっても良く、実施例の項で述べる分
子量範囲に限定されない。Also, 2-[trimethoxy]silyl-1,3-butadiene, 2-[methoxydimethyl]silyl-1,3-butadiene, 2-[dimethoxymethyl]silyl-1,3-butadiene, 2-[trichloro]silyl-1. The molecular weight of the polymer of the present invention, which also includes 3-butadiene, 2-[dimethylchloro]silyl-1,3-butadiene, etc., is not limited and may be either a polymer or an oligomer, and the molecular weight described in the Examples section Not limited to range.
本発明重合体の製造方法は、ラジカル重合、カチオン重
合又はアニオン重合の何れの方法も採用出来る。The method for producing the polymer of the present invention can be any of radical polymerization, cationic polymerization, and anionic polymerization.
ラジカル重合の開始剤としては、単なる高温加熱及び光
照射、２．２−アゾビスイソブチロニトリル等のアゾ系
開始剤、ベンゾイルパーオキサイド等のパーオキサイド
系開始剤或いはベンゾイルパーオキサイドとＮ、Ｎ−ジ
メチルアニリンの組合せ等のレドックス系開始剤等が挙
げられる。Initiators for radical polymerization include simple high-temperature heating and light irradiation, azo initiators such as 2.2-azobisisobutyronitrile, peroxide initiators such as benzoyl peroxide, or benzoyl peroxide and N,N. - redox initiators such as a combination of dimethylaniline and the like.
カチオン重合の開始剤としては、塩化アルミニウム、三
弗化硼素及びジクロロモノエチルアルミニウム等のルイ
ス酸系開始剤等が挙げられる。Examples of initiators for cationic polymerization include Lewis acid initiators such as aluminum chloride, boron trifluoride, and dichloromonoethylaluminum.
アニオン重合の開始剤としては、ナトリウム−ナフタレ
ン・ラジカルイオン対、ｎ−ブチルリチウム等のアルキ
ル金属及び金属ナトリウム等のアルカリ金属単体、チー
グラー系触媒等が挙げられる。Examples of initiators for anionic polymerization include sodium-naphthalene radical ion pairs, alkyl metals such as n-butyllithium, simple alkali metals such as metallic sodium, Ziegler catalysts, and the like.
然し、単なる高温加熱では重合度は低かった。However, simply heating at a high temperature resulted in a low degree of polymerization.
以上の重合反応は、置換−１，３−ブタジエン誘導体に
開始剤を加え直接重合重合反応を行っても良く、重合反
応を阻害しない溶剤中で重合反応を行っても良い。The above polymerization reaction may be carried out directly by adding an initiator to the substituted-1,3-butadiene derivative, or may be carried out in a solvent that does not inhibit the polymerization reaction.
かかる溶剤としては、ラジカル重合ではトルエン、酢酸
エチル等が好ましく、カチオン重合では、四塩化炭素、
クロロホルム等のハロゲン化炭化水素等が好ましい、又
、アニオン重合では、脱水したテトラヒドロフランやジ
オキサン等のエーテル系溶剤の使用が好ましい。As such a solvent, toluene, ethyl acetate, etc. are preferable for radical polymerization, and carbon tetrachloride, ethyl acetate, etc. are preferable for cationic polymerization.
Halogenated hydrocarbons such as chloroform are preferred, and in anionic polymerization, it is preferred to use dehydrated ether solvents such as tetrahydrofuran and dioxane.
以下、本発明について実施例を挙げて更に詳細に説明す
る。Hereinafter, the present invention will be explained in more detail by giving examples.
実施例１
ガラス製アンプルに、薄情した２−メトキシシリル−１
，３−ブタジエン５．２２ｇ （３Ｘ１０−”モル）と
アゾイソブチロニトリル０．０３ｇ （１，８ｘｌＯ−
４モル）を入れて封管し、６０℃の恒温槽内に浸し１０
時間反応させた。Example 1 2-methoxysilyl-1 in a glass ampoule
, 5.22 g (3X10-" mole) of 3-butadiene and 0.03 g of azoisobutyronitrile (1,8x1O-"
4 mol), sealed the tube, and immersed it in a constant temperature bath at 60℃ for 10 minutes.
Allowed time to react.
反応後封管を割って、内容物を真空乾燥して重合体を得
た。After the reaction, the sealed tube was broken and the contents were vacuum dried to obtain a polymer.
得られた重合体を、テトラヒドロフラン溶液としてゲル
バーミニ−シランクロマトグラフィー法で分子量を測定
した結果、重量平均分子量は５２００であった。The weight average molecular weight of the obtained polymer was measured as a tetrahydrofuran solution by gel vermini-silane chromatography, and the weight average molecular weight was 5,200.
又、ガラス転移温度を示差熱分析法（昇温速度１０℃／
＋ｍ１ｎ）で測定したところ一４３℃であった。In addition, the glass transition temperature was determined by differential thermal analysis (heating rate 10℃/
+m1n) and the temperature was -43°C.
実施例２
２−メトキシシリル−１，３−ブタジエン５．２２ｇ（
３Ｘ１０−”モル）、酢酸エチル２ｍｌ、ベンゾイルパ
ーオキサイド０．１ｇ （４，ｌＸｌ０−’モル）及び
Ｎ、Ｎ−ジメチルアニリン０．Ｉｇ Ｃ８，３ＸＩＯ−
’モル）を２４時間反応させた他は、実施例１と同様に
重合反応及び処理を行った。Example 2 5.22 g of 2-methoxysilyl-1,3-butadiene (
3X10-'' mol), 2 ml ethyl acetate, 0.1 g benzoyl peroxide (4,1X10-'' mol) and 0.Ig N,N-dimethylaniline C8,3XIO-
The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that the mol) was reacted for 24 hours.
得られた重合体の分子量は９５０００であった。The molecular weight of the obtained polymer was 95,000.
又、ガラス転移温度は、−４３℃であった。Moreover, the glass transition temperature was -43°C.
実施例３
２−メトキシシリル−１，３−ブタジエン５．２２ｇ（
３ＸＩＯ−”モル）と金属ナトリウム０．０４ｇ（１，
７Ｘ１０−’モル）を１６時間反応させ、内容物を脱水
メタノールで沈澱させた他は実施例１と同様に重合反応
及び処理を行った。Example 3 5.22 g of 2-methoxysilyl-1,3-butadiene (
3XIO-”mol) and 0.04g (1,
The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that 7×10-' mol) was reacted for 16 hours and the contents were precipitated with dehydrated methanol.
得られた重合体の分子量は７００００であった。The molecular weight of the obtained polymer was 70,000.
又、ガラス転移温度は、−４３℃であった。Moreover, the glass transition temperature was -43°C.
実施例４
２−メトキシシリル−１，３−ブタジエン５．２２ｇ（
３Ｘ １０−”モル）と三弗化硼素−エーテル付加物０
．０５ｇ （３，５ｘｌＯ−’モル）を１６時間反応さ
せ他は実施例１と同様に重合反応及び処理を行った。Example 4 5.22 g of 2-methoxysilyl-1,3-butadiene (
3X 10-” mol) and boron trifluoride-ether adduct 0
．． The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that 05g (3.5xlO-' mol) was reacted for 16 hours.
得られた重合体の分子量は２７０００であった。The molecular weight of the obtained polymer was 27,000.
又、ガラス転移温度は、−４３℃であった。Moreover, the glass transition temperature was -43°C.
実施例５
２−トリクロロシリル−１，３−ブタジエン５．６３ｇ
（３ＸＩＯ−”モル）と三弗化硼素・エーテル付加物０
．０５ｇ （３，５ｘｔｏ−’モル）を１６時間反応さ
せた他は、実施例１と同様に重合反応及び処理を行った
。Example 5 2-trichlorosilyl-1,3-butadiene 5.63g
(3XIO-”mol) and boron trifluoride/ether adduct 0
．． The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that 05 g (3.5 x to'mol) was reacted for 16 hours.
得られた重合体の分子量は、１５０００であった。The molecular weight of the obtained polymer was 15,000.
実施例６
２−（メトキシジメチル）シリル−１，３−ブタジエン
４．２６ｇ （３ｘｌＯ−”モル）と金属ナトリウム
０．０４ｇ （１，７ｘｌＯ−’モル）を２４時間反応
させ、内容物を脱水メタノールで沈澱させた他は実施例
１と同様に重合反応及び処理を行った。Example 6 4.26 g (3xlO-' mol) of 2-(methoxydimethyl)silyl-1,3-butadiene and 0.04 g (1,7xlO-' mol) of metallic sodium were reacted for 24 hours, and the contents were dissolved in dehydrated methanol. The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that the precipitation was carried out in Example 1.
得られた重合体の分子量は、３７０００であった。The molecular weight of the obtained polymer was 37,000.
Claims (1)
誘導体を重合する事によって得られる重合体 ▲数式、化学式、表等があります▼〔１〕 （Ｘは、水素又はＳｉＲ＿１Ｒ＿２Ｒ＿３を示し、Ｘの
１つは必ずＳｉＲ＿１Ｒ＿２Ｒ＿３である、又、Ｒ＿１
、Ｒ＿２、Ｒ＿３は、ハロゲン、低級アルコキシ基又は
低級アルキル基を示し、Ｒ＿１、Ｒ＿２、Ｒ＿３が同時
に低級アルキル基である場合を除く。） ２、構造式〔１〕で表される置換−１，３−ブタジエン
誘導体をラジカル重合、カチオン重合又はアニオン重合
する事による重合体の製造方法[Scope of Claims] 1. A polymer obtained by polymerizing a substituted-1,3-butadiene derivative represented by the structural formula [1] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [1] (X is , hydrogen or SiR_1R_2R_3, one of X is always SiR_1R_2R_3, and R_1
, R_2, and R_3 represent a halogen, a lower alkoxy group, or a lower alkyl group, except when R_1, R_2, and R_3 are all lower alkyl groups. ) 2. Method for producing a polymer by radical polymerization, cationic polymerization or anionic polymerization of a substituted-1,3-butadiene derivative represented by structural formula [1]
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030785A JPS61168605A (en) | 1985-01-23 | 1985-01-23 | Polymer of substituted 1,3-butadiene derivative and its production |
| DE8686100763T DE3670642D1 (en) | 1985-01-23 | 1986-01-21 | POLYMERS OF SUBSTITUTED 1,3-BUTADIENE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF. |
| EP86100763A EP0189174B1 (en) | 1985-01-23 | 1986-01-21 | Polymers of substituted 1,3-butadiene compounds and process for their preparation |
| US06/824,581 US4730031A (en) | 1985-01-23 | 1986-01-23 | Polymers of substituted 1,3-butadiene compounds having reactive silyl groups and process for their preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030785A JPS61168605A (en) | 1985-01-23 | 1985-01-23 | Polymer of substituted 1,3-butadiene derivative and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61168605A true JPS61168605A (en) | 1986-07-30 |
| JPH0518847B2 JPH0518847B2 (en) | 1993-03-15 |
Family
ID=11746589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1030785A Granted JPS61168605A (en) | 1985-01-23 | 1985-01-23 | Polymer of substituted 1,3-butadiene derivative and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61168605A (en) |
-
1985
- 1985-01-23 JP JP1030785A patent/JPS61168605A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0518847B2 (en) | 1993-03-15 |
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