JPH0518847B2 - - Google Patents
Info
- Publication number
- JPH0518847B2 JPH0518847B2 JP1030785A JP1030785A JPH0518847B2 JP H0518847 B2 JPH0518847 B2 JP H0518847B2 JP 1030785 A JP1030785 A JP 1030785A JP 1030785 A JP1030785 A JP 1030785A JP H0518847 B2 JPH0518847 B2 JP H0518847B2
- Authority
- JP
- Japan
- Prior art keywords
- butadiene
- mol
- silyl
- molecular weight
- polymer
- 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.)
- Expired - Lifetime
Links
- -1 substituted- 1,3 - butadiene Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 8
- BQIZQWJZCWVEGF-UHFFFAOYSA-N buta-1,3-dienylsilane Chemical compound [SiH3]C=CC=C BQIZQWJZCWVEGF-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- GSUTWAUZKRUMPD-UHFFFAOYSA-N buta-1,3-dien-2-yl(methoxy)silane Chemical compound CO[SiH2]C(=C)C=C GSUTWAUZKRUMPD-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- DEMRFFKCHVQCFJ-UHFFFAOYSA-N buta-1,3-dien-2-yl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)C(=C)C=C DEMRFFKCHVQCFJ-UHFFFAOYSA-N 0.000 description 2
- HWCCZVRBWGLIGI-UHFFFAOYSA-N buta-1,3-dien-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(=C)C=C HWCCZVRBWGLIGI-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000006732 Torreya nucifera Nutrition 0.000 description 1
- 244000111306 Torreya nucifera Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FJIHDNQJJPBXOD-UHFFFAOYSA-N buta-1,3-dien-2-yl(dimethoxymethyl)silane Chemical compound COC(OC)[SiH2]C(=C)C=C FJIHDNQJJPBXOD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、置換−１，３−ブタジエン誘導体を
重合することによつ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。
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
合物が多かつた。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
されることはほとんどなく、他のプラスチツクの
改質の目的で少量共重合される程度であつた。
本発明者は、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
に展開可能なことを知見し、本発明を完成したも
のである。
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、無機フイラー表面にゴム弾
性を付加しプラスチツクの耐衝撃性の改良、磁性
体表面にゴム弾性を付加することによる高配向性
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、無機フイラー
表面を処理することによるFRP等の耐加水分解
性の改良、ガラス、セラミツクス、ゴム製品の接
着剤及びカツプリング剤等の用途に使用でき、そ
の他各種の用途展開が可能である。
更に場合によつては、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
することもできる。
又、従来のシランカツプリング剤と同様な用途
にも使用できる。
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〔〕
で表される置換−１，３−ブタジエン誘導体を重
合することにより、繰り返し単位として
The present invention relates to a novel polymer obtained by polymerizing substituted-1,3-butadiene derivatives and a method for producing the same, and in particular, a diene polymer having a reactive silyl group and its production. It is about the method. Conventional reactive silane compounds are often used for the purpose of surface treatment of inorganic materials, and most of them are low-molecular compounds. In addition, there are polymerizable silane compounds such as vinyl compounds and methacrylic acid compounds that have reactive silyl groups, but these are rarely polymerized alone and are copolymerized in small amounts for the purpose of modifying other plastics. It was at a level where it was possible to do so. The present inventor 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 developed for various uses. 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 and coupling agent for products, and can be used in a variety of other applications. Further, depending on the case, a substituted 1,3-butadiene derivative monomer can be added to the above substance and then heated and polymerized. It can also be used for the same purposes as conventional silane coupling agents. The novel diene polymer having a reactive silyl group of the present invention has the structural formula [] By polymerizing the substituted-1,3-butadiene derivative represented by
【式】【formula】
【式】【formula】
【式】及び[Formula] and
【式】
（式中、ＸはSiR1R2R3を示し、R1、R2、R3は、
ハロゲン、炭素数１〜３のアルコキシ基又は炭素
数１〜３のアルキル基を示し、R1、R2、R3が同
時にアルキル基である場合を除く、又ａ、ｂ、ｃ
及びｄは各繰り返し単位の重量％を示し、ａ＝50
〜100、ｂ＝０〜50、ｃ＝０〜50、ｄ＝０〜50で
ある。）
から成る、分子量が5000〜10万である重合体とな
る。
本発明に用いる置換−１，３−ブタジエン誘導
体としては、１−〔トリメトキシ〕シリル−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、１−〔トリク
ロロ〕シリル−１，３−ブタジエン、１−〔ジメ
チルクロロ〕シリル−１，３−ブタジエン等が挙
げられる。
又、２−〔トリメトキシ〕シリル−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−１，３−ブタジエン、２−〔ジメチルクロ
ロ〕シリル−１，３−ブタジエン等も挙げられ
る。
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
できる。
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
合せ等のレドツクス系開始剤等が挙げられる。
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。
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。
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つて
も良く、重合反応を阻害しない溶剤中で重合反応
を行つても良い。
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。
こうして得られる置換１，３−ブタジエン誘導
体の重合体は、イソプレン等のジエン系重合体同
様にシス−１，４結合、トランス−１，４結合、
１，２結合、３，４結合の４つの異性体を生じる
が、前記の通常の重合方法では、通常のジエン系
重合体同様１，４結合の生成が優先的である。
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。
実施例 １
ガラス製アンプルに、蒸溜した２−メトキシシ
リル−１，３−ブタジエン5.22ｇ（３×10-2モ
ル）とアゾイソブチロニトリル0.03ｇ（1.8×10-4
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。
反応後封管を割つて、内容物を真空乾燥して重
合体を得た。
得られた重合体を、テトラヒドロフラン溶液と
してゲルパーミエーシヨンクロマトグラフイー法
で分子量を測定した結果、重量平均分子量は5200
であつた。
又、ガラス転移温度を示差熱分析法（昇温速度
10℃／min）で測定したところ−43℃であつた。
実施例 ２
２−メトキシシリル−１，３−ブタジエン5.22
ｇ（３×10-2モル）、酢酸エチル２ml、ベンゾイ
ルパーオキサイド0.1ｇ（4.1×10-4モル）及びＮ，
Ｎ−ジメチルアニリン0.1ｇ（8.3×10-4モル）を
24時間反応させた他は、実施例１と同様に重合反
応及び処理を行つた。
得られた重合体の分子量は95000であつた。
又、ガラス転移温度は、−43℃であつた。
実施例 ３
２−メトキシシリル−１，３−ブタジエン5.22
ｇ（３×10-2モル）と金属ナトリウム0.04ｇ（1.7
×10-3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
反応及び処理を行つた。
得られた重合体の分子量は70000であつた。
又、ガラス転移温度は、−43℃であつた。
実施例 ４
２−メトキシシリル−１，３−ブタジエン5.22
ｇ（３×10-2モル）と三弗化硼素−エーテル付加
物0.05ｇ（3.5×10-4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つた。
得られた重合体の分子量は27000であつた。
又、ガラス転移温度は、−43℃であつた。
実施例 ５
２−トリクロロシリル−１，３−ブタジエン
5.63ｇ（３×10-2モル）と三弗化硼素・エーテル
付加物0.05ｇ（3.5×10-4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
つた。
得られた重合体の分子量は、15000であつた。
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（３×10-2モル）と金属ナトリウ
ム0.04ｇ（1.7×10-3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つた。
得られた重合体の分子量は、37000であつた。
実施例 ７
２−トリメトキシシリル−１，３−ブタジエン
100ｇ（0.575モル）とカヤエステル（化薬ヌー
リー〓製、ｔ−ブチルパーオキシイソブチレー
ト）２ｇ（0.0125モル）をフラスコに仕込み、90
℃の恒温槽内に浸し３時間40分反応させた他は、
実施例１と同様に処理を行つた。
得られた重合体の収率は85％で重量平均分子量
は32000であつた。[Formula] (In the formula, X represents SiR 1 R 2 R 3 , and R 1 , R 2 , R 3 are
Indicates a halogen, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, except when R 1 , R 2 , and R 3 are simultaneously alkyl groups, and a, b, c
and d indicate the weight% of each repeating unit, a=50
~100, b=0-50, c=0-50, d=0-50. ) and has a molecular weight of 5,000 to 100,000. The substituted-1,3-butadiene derivatives used in the present invention include 1-[trimethoxy]silyl-1,
3-butadiene, 1-[methoxydimethyl]silyl-1,3-butadiene, 1-[dimethoxymethyl]silyl-1,3-butadiene, 1-[trichloro]silyl-1,3-butadiene, 1-[dimethylchloro] ] Silyl-1,3-butadiene and the like. Also, 2-[trimethoxy]silyl-1,3-butadiene, 2-[methoxydimethyl]silyl-1,
Also included are 3-butadiene, 2-[dimethoxymethyl]silyl-1,3-butadiene, 2-[trichloro]silyl-1,3-butadiene, 2-[dimethylchloro]silyl-1,3-butadiene, and the like. The method for producing the polymer of the present invention can be any of radical polymerization, cationic polymerization, and anionic polymerization. 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. - dimethylaniline combination, etc., and the like. Examples of initiators for cationic polymerization include Lewis acid initiators such as aluminum chloride, boron trifluoride, and dichloromonoethylaluminum. As an initiator for anionic polymerization, sodium-
Examples include naphthalene radical ion pairs, alkyl metals such as n-butyllithium, simple alkali metals such as sodium metal, Ziegler catalysts, and the like. 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. As such a solvent, toluene, ethyl acetate, etc. are preferable for radical polymerization, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, etc. are preferable for cationic polymerization. Further, in anionic polymerization, it is preferable to use an ether solvent such as dehydrated tetrahydrofuran or dioxane. The substituted 1,3-butadiene derivative polymer thus obtained has cis-1,4 bonds, trans-1,4 bonds,
Four isomers, 1,2 bonds and 3,4 bonds, are produced, but in the above-mentioned normal polymerization method, the production of 1,4 bonds is preferential, as in normal diene polymers. Hereinafter, the present invention will be explained in more detail by giving examples. Example 1 In a glass ampoule, 5.22 g (3 x 10 -2 mol) of distilled 2-methoxysilyl-1,3-butadiene and 0.03 g (1.8 x 10 -4 mol) of azoisobutyronitrile were added.
mol), seal the tube, and immerse it in a constant temperature bath at 60℃ for 10 minutes.
Allowed time to react. After the reaction, the sealed tube was broken and the contents were vacuum dried to obtain a polymer. The molecular weight of the obtained polymer was measured using gel permeation chromatography as a solution in tetrahydrofuran, and the weight average molecular weight was 5200.
It was hot. In addition, the glass transition temperature can be determined by differential thermal analysis (heating rate
When measured at a rate of 10°C/min), the temperature was -43°C. Example 2 2-methoxysilyl-1,3-butadiene 5.22
g (3 x 10 -2 mol), 2 ml of ethyl acetate, 0.1 g (4.1 x 10 -4 mol) of benzoyl peroxide and N,
0.1g (8.3×10 -4 mol) of N-dimethylaniline
The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that the reaction was carried out for 24 hours. The molecular weight of the obtained polymer was 95,000. Moreover, the glass transition temperature was -43°C. Example 3 2-methoxysilyl-1,3-butadiene 5.22
g (3×10 -2 mol) and metallic sodium 0.04 g (1.7
The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that 10 -3 mol) was reacted for 16 hours and the contents were precipitated with dehydrated methanol. The molecular weight of the obtained polymer was 70,000. Moreover, the glass transition temperature was -43°C. Example 4 2-methoxysilyl-1,3-butadiene 5.22
(3×10 −2 mol) and 0.05 g (3.5×10 −4 mol) of boron trifluoride-ether adduct were reacted for 16 hours, and the polymerization reaction and treatment were carried out in the same manner as in Example 1 except for the reaction. The molecular weight of the obtained polymer was 27,000. Moreover, the glass transition temperature was -43°C. Example 5 2-trichlorosilyl-1,3-butadiene
The polymerization reaction and treatment were carried out in the same manner as in Example 1, except that 5.63 g (3 × 10 -2 mol) and 0.05 g (3.5 × 10 -4 mol) of boron trifluoride/ether adduct were reacted for 16 hours. Ivy. The molecular weight of the obtained polymer was 15,000. Example 6 4.26 g (3 x 10 -2 mol) of 2-(methoxydimethyl)silyl-1,3-butadiene and 0.04 g (1.7 x 10 -3 mol) of metallic sodium were reacted for 24 hours, and the contents were dissolved in dehydrated methanol. Example 1 except that precipitation was performed with
The polymerization reaction and treatment were carried out in the same manner as above. The molecular weight of the obtained polymer was 37,000. Example 7 2-trimethoxysilyl-1,3-butadiene
100 g (0.575 mol) and 2 g (0.0125 mol) of Kaya ester (manufactured by Kayaku Nouri Co., Ltd., t-butylperoxyisobutyrate) were charged in a flask, and the
Other than immersing it in a constant temperature bath at ℃ and reacting for 3 hours and 40 minutes,
The treatment was carried out in the same manner as in Example 1. The yield of the obtained polymer was 85% and the weight average molecular weight was 32,000.
Claims (1)
合することにより、繰り返し単位として 【式】 【式】 【式】及び【式】 （式中、ＸはSiR1R2R3を示し、R1、R2、R3は、
ハロゲン、炭素数１〜３のアルコキシ基又は炭素
数１〜３のアルキル基を示し、R1、R2、R3が同
時にアルキル基である場合を除く、又ａ、ｂ、
ｃ、及びｄは各繰り返し単位の重量％を示し、ａ
＝50〜100、ｂ＝０〜50、ｃ＝０〜50、ｄ＝０〜
50である。） から成る、分子量が5000〜10万である重合体。[Claims] 1. Structural formula [] By polymerizing substituted- 1,3 - butadiene derivatives represented by 1 , R2 , R3 are
Indicates a halogen, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, except when R 1 , R 2 , and R 3 are all alkyl groups, and a, b,
c and d indicate the weight % of each repeating unit, a
=50~100, b=0~50, c=0~50, d=0~
It is 50. ) with a molecular weight of 5,000 to 100,000.
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 |
| EP86100763A EP0189174B1 (en) | 1985-01-23 | 1986-01-21 | Polymers of substituted 1,3-butadiene compounds and process for their preparation |
| DE8686100763T DE3670642D1 (en) | 1985-01-23 | 1986-01-21 | POLYMERS OF SUBSTITUTED 1,3-BUTADIENE COMPOUNDS AND METHOD FOR THE PRODUCTION THEREOF. |
| 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 JPS61168605A (en) | 1986-07-30 |
| JPH0518847B2 true 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 |
|---|---|
| JPS61168605A (en) | 1986-07-30 |
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