JPS6270405A - Telechelic vinyl polymer having alkoxysilyl group and its production - Google Patents
Telechelic vinyl polymer having alkoxysilyl group and its productionInfo
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- JPS6270405A JPS6270405A JP21166785A JP21166785A JPS6270405A JP S6270405 A JPS6270405 A JP S6270405A JP 21166785 A JP21166785 A JP 21166785A JP 21166785 A JP21166785 A JP 21166785A JP S6270405 A JPS6270405 A JP S6270405A
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Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアルコキシシリル基を有するテレケリツク(t
el echel ic)なビニルポリマー1更ニ詳シ
くは、その分子両末端に存在するアルコキシシリル基の
縮合によって物理的強度に優れた架橋性樹脂となり、塗
料、接着剤、シール材、粘着剤等に利用しうるビニルポ
リマーおよびその製法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to telechelics (t) having an alkoxysilyl group.
In detail, the condensation of the alkoxysilyl groups present at both ends of the molecule results in a crosslinkable resin with excellent physical strength, which can be used in paints, adhesives, sealants, pressure-sensitive adhesives, etc. This invention relates to a vinyl polymer that can be used for and a method for producing the same.
従来技術と解決すべき問題点
従来より、耐候性、耐熱性、耐薬品性に優れた樹脂とし
てシリコーン樹脂がよく知られているが、その原料コス
トが高くつくなどの理由から繁用樹脂として使用されて
いない。このことから、さまざまな樹脂に反応性のシリ
ル基を導入する試みがなされている。実用化されている
ものとして、ポリプロプレンゲリコール(PPG)の分
子両末端にアルコキシシリル基を導入したものが知られ
ているが、主鎖がPPGであるため耐候性、耐熱性に劣
る。Conventional technology and problems to be solved Silicone resin has long been well known as a resin with excellent weather resistance, heat resistance, and chemical resistance, but due to the high cost of its raw materials, it is used as a commonly used resin. It has not been. For this reason, attempts have been made to introduce reactive silyl groups into various resins. A known product that has been put into practical use is polypropylene gellicol (PPG) with alkoxysilyl groups introduced at both ends of the molecule, but because the main chain is PPG, it has poor weather resistance and heat resistance.
一方、アクリル樹脂は耐候性、耐熱性に優れた樹脂とし
て知られ、塗料や成型品などに多用されている。近年、
アクリル樹脂の機能化を計る目的で、アクリル樹脂にさ
まざまな官能基を導入することが試みられてきた。例え
ば、アクリル系モノマーをラジカル重合で官能基を有す
る他のモノマーと共重合させ、ポリマー側鎖に目的とす
る官能基を導入する方法、これ以外に官能基を有する連
鎖移動剤や開始剤を用い、ポリマー末端に官能基を導入
する方法が知られている。しかし、いずれの方法にあっ
ても、両末端に反応性のシリル基を有するテレケリツク
なビニルポリマーの合成は困難である。On the other hand, acrylic resin is known as a resin with excellent weather resistance and heat resistance, and is often used in paints, molded products, etc. recent years,
In order to functionalize acrylic resins, attempts have been made to introduce various functional groups into acrylic resins. For example, a method of copolymerizing an acrylic monomer with another monomer having a functional group by radical polymerization to introduce the desired functional group into the polymer side chain, or using a chain transfer agent or initiator having a functional group. , a method of introducing a functional group at the end of a polymer is known. However, with either method, it is difficult to synthesize a telechelic vinyl polymer having reactive silyl groups at both ends.
また、イオン重合系においてポリメタクリル酸エステル
の末端ヘシリル基をi人することに成功している。しか
し、この方法は開始剤系が複雑であり、モノマーとして
メタクリル酸メチルしか使用できず1反応条件のコント
ロールが難しいため実用化には適さない。In addition, in an ionic polymerization system, the terminal hesylyl group of polymethacrylic acid ester has been successfully modified. However, this method is not suitable for practical use because the initiator system is complicated, only methyl methacrylate can be used as a monomer, and it is difficult to control the reaction conditions.
そこで本発明者らは、上述の耐候性、耐熱性に優れたア
クリル樹脂の両末端に反応性のシリル基を簡単に導入す
る方法について鋭意研究を進めた結果、アルコキシシリ
ル基を有するジスルフィド化合物と、アクリル系モノマ
ーを含む各種のビニル系モノマーとを使用し、これらを
光重合反応に供すれば、目的とする両末端にアルコキシ
シリル基を導入したテレケリツクなビニルポリマーが得
られることを見出し、本発明を完成させるに至った。Therefore, the present inventors conducted extensive research into a method for easily introducing reactive silyl groups at both ends of the above-mentioned acrylic resin, which has excellent weather resistance and heat resistance. discovered that by using various vinyl monomers including acrylic monomers and subjecting them to photopolymerization, it was possible to obtain telechelic vinyl polymers with alkoxysilyl groups introduced at both ends. The invention was completed.
発明の構成と効果
すなわち、本発明は、式:
〔式中、R1およびR2は同一もしくは異なっテ炭素数
1〜4のアルキル、R3は炭素数1〜4のアルキレン、
およびnはO〜2の整数である〕で示されるジスルフィ
ド化合物の1種または2種以上と、式:
または
Y3
〔式中、k は水素またはメチル、Yl は炭素数2〜
11のエステル基、フェニルまたはハロゲン、Y2は炭
素数2〜6のエステル基またはハロゲン、およびY3
は弗素または塩素である〕で示されるビニル系モノマー
の1種または2種以上との光重合反応1こよって得られ
る、式:〔式中、R1、i2 、R3およびnは前記と
同意義。Structure and Effects of the Invention That is, the present invention provides the following features: [wherein R1 and R2 are the same or different, alkyl having 1 to 4 carbon atoms, R3 is alkylene having 1 to 4 carbon atoms,
and n is an integer of 0 to 2], and one or more disulfide compounds represented by the formula: or Y3 [wherein k is hydrogen or methyl, and Yl has 2 to 2 carbon atoms]
11 ester group, phenyl or halogen, Y2 is an ester group or halogen having 2 to 6 carbon atoms, and Y3
is fluorine or chlorine] is obtained by photopolymerization reaction 1 with one or more vinyl monomers represented by the formula: [wherein R1, i2, R3 and n have the same meanings as above.
前記と同意義)の少なくとも17で構成され、mは10
〜10000 である〕
で示されることを特徴とする分子両末端番こアルコキシ
シリル基を有するビニルポリマーを提供するものである
。(same meaning as above), m is 10
to 10,000] The present invention provides a vinyl polymer having alkoxysilyl groups at both ends of the molecule.
本発明で用いる」二記ジスルフィド化合物としては、例
えば
ビス(トリメ(1)トキシシリルメチル)ジスルフィド
、
ビス(トリメ(1)トキシシリルエチル)ジスルフィド
、
ビス(トリメ(1)トキシシリルプロピル〕ジスルフィ
ド、
ビス(トリメ(1)トキシシリルブチル)ジスルフィド
、
ビス(メチルジメ(1)トキシシリルメチル)ジスルフ
ィド、
ビス(メチルジメ(1)トキシシリルエチル)ジスルフ
ィド、
ビス(メチルジメ(1)トキシシリルプロピル)ジスル
フィド、
ビス(メチルジメ(1)トキシシリルブチル)ジスルフ
ィド、
ビス(エチルジメ(1)トキシシリルメチル)ジスルフ
ィド、
ビス(エチルジメ(1)トキシシリルエチル)ジスルフ
ィド、
ビス(エチルジメ(1)トキシシリルプロピル)ジスル
フィド、
ビス(エチルジメ(工〕トキシシリルブチル)ジスルフ
ィド、
ビス(プロビルジメ(1)トキシシリルメチル)ジスル
フィド、
ビス(プロピルジメ(1)トキシシリルエチル)ジスル
フィド、
ビス(フロピルジメ(1)トキシシリルプロヒル)ジス
ルフィド、
ビス(プロピルジメ(1)トキシシリルブチル)ジスル
フィド、
ビス(ジメチレン(1)トキシシリルメチル〕ジスルフ
ィド、
ビス(ジメチレン(1)トキシシリルエチル)ジスルフ
ィド、
ビス(ジメチレン(1)トキシシリルプロピル)ジスル
フィド、
ビス(ジメチレン(1)トキシシリルブチル)ジスルフ
ィド、
ビス(ジエチルメ(工〕トキシシリルメチル)ジスルフ
ィド、
ビス(ジエチルメ(1)トキシシリルエチル)ジスルフ
ィド。Examples of the di-disulfide compounds used in the present invention include bis(trimeth(1)toxysilylmethyl)disulfide, bis(trimeth(1)toxysilylethyl)disulfide, bis(trimeth(1)toxysilylpropyl)disulfide, bis(trimeth(1)toxysilylpropyl)disulfide), (trimeth(1)toxysilylbutyl)disulfide, bis(methyldime(1)toxysilylmethyl)disulfide, bis(methyldime(1)toxysilylethyl)disulfide, bis(methyldime(1)toxysilylpropyl)disulfide, bis(methyldime(1)toxysilylpropyl)disulfide, bis(methyldime(1)toxysilylpropyl)disulfide, (1) toxysilylbutyl) disulfide, bis(ethyldime(1) toxysilylmethyl) disulfide, bis(ethyldime(1) toxysilylethyl) disulfide, bis(ethyldime(1) toxysilylpropyl) disulfide, bis(ethyldime(1) toxysilylpropyl) disulfide, ] Toxysilylbutyl) disulfide, bis(propyldime(1) toxysilylmethyl) disulfide, bis(propyldime(1) toxysilylethyl) disulfide, bis(furopyldime(1) toxysilylproyl) disulfide, bis(propyldime(1) toxysilylproyl) disulfide, Toxysilylbutyl) disulfide, bis(dimethylene(1)toxysilylmethyl)disulfide, bis(dimethylene(1)toxysilylethyl)disulfide, bis(dimethylene(1)toxysilylpropyl)disulfide, bis(dimethylene(1)toxysilyl) butyl) disulfide, bis(diethylmeth(1)toxysilylethyl)disulfide, bis(diethylmeth(1)toxysilylethyl)disulfide.
ビス(ジエチルメ(1)トキシシリルプロピル)ジスル
フィド、
ビス(ジエチルメ(1)トキシシリルブチル〕ジスルフ
ィド、
ビス(ジプロピルメ(1)トキシシリルメチル)ジスル
フィド、
ビス(ジプロピルメ(工〕トキシシリルエチル〕ジスル
フィド、
ビス(ジプロピルメ(1)トキシシリルプロピル)ジス
ルフィド、
ビス(ジプロビルメ(1)トキシシリルブチル)ジスル
フィド
等が挙げられ、これらの1種または2種以」―を重合に
供する。なお、上記「メ(1)トキシ」とはメトキシま
たはエトキシを指称する。Bis(diethylmeth(1)toxysilylpropyl)disulfide, Bis(diethylmeth(1)toxysilylbutyl)disulfide, Bis(dipropylmeth(1)toxysilylmethyl)disulfide, Bis(dipropylmeth(ethoxysilylethyl)disulfide, Bis(diethylmeth(1)toxysilylbutyl)disulfide, Examples include dipropylame(1) toxysilylpropyl) disulfide, bis(dipropylame(1) toxysilylbutyl) disulfide, and one or more of these are subjected to polymerization. ” refers to methoxy or ethoxy.
本発明で用いる」1記ビニル系モノマーとしては、例え
ばアクリル酸エステル類(アクリル酸エチル、アクリル
酸ブチル、アクリル酸2−エチルヘキシル、アクリル酸
プロピル、アクリル酸ヘン−f−/I/、アクリル酸ス
テアリルなど)、メタクリル酸エステル類(メタクリル
酸メチル、メタクリル酸エチル、メタクリル酸ブチル、
メタクリル酸2−エチルヘキシル、メタクリル酸ラウリ
ル、メタクリル酸ベンジル、メタクリル酸シクロヘキシ
ルなど)。Examples of vinyl monomers used in the present invention include acrylic esters (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, propyl acrylate, hene-f-/I/acrylate, stearyl acrylate). ), methacrylate esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate,
2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, etc.).
スチレンもしくはその誘導体(α−メメチスチレン、ク
ロルメチルスチレンなど)、フタル酸ジエステル類(フ
タル酸ジエチル、≠≠#犠澤リーす叫フタル酸ジブチル
、フタル酸ジプロピルなど)、ハロゲン1ヒビニル類(
塩IISビニル、塩化ビニリデン、フッ比エチi/ン、
フッ化ビニリデン、フッ(Bビニレンなど)等が挙げら
れ、これらの1種または2種以上を重合に供する。Styrene or its derivatives (α-memethystyrene, chloromethylstyrene, etc.), phthalate diesters (diethyl phthalate, dibutyl phthalate, dipropyl phthalate, etc.), halogens (
IIS vinyl salt, vinylidene chloride, fluoroethylene,
Examples include vinylidene fluoride, fluoride (B-vinylene, etc.), and one or more of these are subjected to polymerization.
本発明]こ係るビニルポリマーは通常、」−記ビニル系
モノマー100部(重量部、以下同様)に対しジスルフ
ィド化合物0.05〜50部を配合し、これを常法fこ
従って光重合に付し、例えば必要に応じて適当な有機溶
媒(トルエン、キシレン、ヘキサン、酢酸エチル、ジオ
クチルフタレートナど)中、常温または5〜60℃の温
度にて4〜30時間光照射を行うことにより製造される
。This invention] This vinyl polymer is usually prepared by blending 0.05 to 50 parts of a disulfide compound with 100 parts (parts by weight, the same applies hereinafter) of the vinyl monomer, and subjecting it to photopolymerization according to a conventional method. For example, it can be produced by irradiating it with light for 4 to 30 hours at room temperature or a temperature of 5 to 60°C in an appropriate organic solvent (toluene, xylene, hexane, ethyl acetate, dioctyl phthalate, etc.) as necessary. Ru.
なお、当該ビニルポリマーの硬化後の樹脂強度を上げた
い場合番こは5」−記ビニル系モノマー100部の内、
アルコキシシリル基を有するモノマー0.1〜10部を
代用することにより5更にポリマー側鎖1こアルコキシ
シリル基を導入せしめ、硬Its後の架橋密度を増大し
て樹脂強度を1−げることかできる。かかるモノマーと
しては、例えばトリメトキシシリルプロピルアクリレー
ト、トリメトキシシリルプロピルメタクリレート、メチ
ルジメトキシシリルプロピルアクリレート、メチルジメ
トキシシリルプロピルメタクリレート、ビニルトリエト
キシシラン、ビニルメチルジェトキシシラン、ビニルジ
メチルエトキシシラン等が挙げられる。In addition, if you want to increase the resin strength after curing of the vinyl polymer, the number 5 is 100 parts of the vinyl monomer,
By substituting 0.1 to 10 parts of a monomer having an alkoxysilyl group, it is possible to further introduce an alkoxysilyl group in the polymer side chain, increase the crosslinking density after hardening, and increase the resin strength. can. Examples of such monomers include trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl acrylate, methyldimethoxysilylpropyl methacrylate, vinyltriethoxysilane, vinylmethyljethoxysilane, vinyldimethylethoxysilane, and the like.
重合系に微量でも水が存在する場合、カルボン酸基やリ
ン酸基やスルホン酸基などの酸基を有するモノマーは使
用できない。もし2これらを水の存在下Cご用いた場合
、重合途中で系全体がゲル化する。If even a trace amount of water is present in the polymerization system, monomers having acid groups such as carboxylic acid groups, phosphoric acid groups, and sulfonic acid groups cannot be used. If two of these are used in the presence of water, the entire system will gel during the polymerization.
次番こ、本発明ビニルポリマーにおける光重合の反応機
構について、下記素反応弐り〜iv)に基づき模式的に
説明する。Next, the reaction mechanism of photopolymerization in the vinyl polymer of the present invention will be schematically explained based on the following elementary reactions 2 to iv).
n) 、SX 十CH2=CRY
RY
Y Y
RR
(但し、Xはアルコキシシリル基を有するアルキル、C
H2,−CRY は一般的なビニル系モノマー)ここ
で、ジスルフィド化合物(xs−sx)はUV光照射に
より簡単に分解され、チイルラジカル(・SX)を生じ
る(式i)。この生じたラジカルの一部がビニル系モノ
マーに付加反応し、開始ラジカルとなる(式i)。さら
にこの開始ラジカルがビニル系モノマーと逐次反応し、
高分子ラジカルとなる(式ii)。この反応は通常のラ
ジカル重合の場合と同じである。ここで生じた高分子ラ
ジカルは系中に存在するチイルラジカルと反応し、−次
ラジカル停止反応により停止し、両末端にアルコキシシ
リル基を有するポリマー(もしくはオリゴマー)となる
(式iv)。通常のラジカル1JI
重合では、停止反応は高分子ラジカル同士の再結合や不
均化反応が優先されるにれは、−次ラジカルの安定性や
反応性が当該チイルラジカルと異なるためである)。な
お、これらの反応機構については、既に大阪而立大学の
大津式らにより提唱されており、他のジスルフィド比合
物を用いた重合系によるテレケリツクなポリマーの合成
が報告されている。n), SX 10CH2=CRY RY Y Y RR (where, X is an alkyl having an alkoxysilyl group, C
H2,-CRY is a general vinyl monomer) Here, the disulfide compound (xs-sx) is easily decomposed by UV light irradiation to generate a thiyl radical (.SX) (Formula i). A part of the generated radical undergoes an addition reaction with the vinyl monomer and becomes an initiating radical (Formula i). Furthermore, this initiating radical reacts with the vinyl monomer sequentially,
It becomes a polymer radical (formula ii). This reaction is the same as in normal radical polymerization. The polymer radicals generated here react with thiyl radicals present in the system and are terminated by a -order radical termination reaction, resulting in a polymer (or oligomer) having alkoxysilyl groups at both ends (Formula iv). In normal radical 1JI polymerization, recombination and disproportionation reactions between polymer radicals are prioritized in the termination reaction because the stability and reactivity of the -order radical differs from that of the thiyl radical). Incidentally, these reaction mechanisms have already been proposed by Shiki Otsu et al. of Osaka Jiritsu University, and the synthesis of telechelic polymers using polymerization systems using other disulfide compounds has been reported.
以上の如くして製造される本発明ビニルポリマーは、そ
の末端部のアルコキシシリル基を縮合させることにより
、機械強度の優れた架橋性樹脂となる。ガラス転移点(
Tg )の高いビニル系モノマーを用いた場合には、塗
料、接着剤などに使用され、またTgの低いビニル系モ
ノマーを用いた場合には、シール材、粘着剤などに使用
することができる。The vinyl polymer of the present invention produced as described above becomes a crosslinkable resin with excellent mechanical strength by condensing the alkoxysilyl groups at the terminal ends. Glass transition point (
When a vinyl monomer with a high Tg) is used, it can be used in paints, adhesives, etc., and when a vinyl monomer with a low Tg is used, it can be used in sealants, adhesives, etc.
次1こ、実施例を挙げて本発明をより具体的に説明する
。Next, the present invention will be explained in more detail with reference to Examples.
実施例1
メカニカルスターシー、冷却管、窒素ガス導入管、温度
計を取り付けた四つロフラスコ1こ、アクリル酸ブチル
223gおよびビス(メチルジメトキシシリルプロピル
)ジスルフィド6ダを入れる。Example 1 223 g of butyl acrylate and 6 damas of bis(methyldimethoxysilylpropyl) disulfide are placed in a four-necked flask equipped with a mechanical starch, a cooling tube, a nitrogen gas inlet tube, and a thermometer.
フラスコ底面より約3c+nの距離に、東芝電機社製S
HL IQQUVランプを設置し、これよりUV光を照
射し、窒素ガスを通じながら重合を行う。At a distance of about 3c+n from the bottom of the flask,
A HL IQQUV lamp is installed, from which UV light is irradiated, and polymerization is carried out while passing nitrogen gas.
この時、重合反応温度が」―がらぬようフラスコのまわ
りを冷却し、重合混合物の温度を15〜20℃に保ちな
がら重合を行う。重合時間と共に反応混合物は増粘し、
約15時間後透明で粘稠な液状ポリマーが得られる。こ
れを取り出し、110℃で4時間減圧乾燥し、その重量
変化法で求めた重合収率は77.2%であった。At this time, the surroundings of the flask are cooled so that the polymerization reaction temperature does not drop, and the polymerization is carried out while maintaining the temperature of the polymerization mixture at 15 to 20°C. As the polymerization time increases, the reaction mixture thickens;
After about 15 hours, a clear, viscous liquid polymer is obtained. This was taken out and dried under reduced pressure at 110° C. for 4 hours, and the polymerization yield determined by the weight change method was 77.2%.
次に、真空乾燥法により残留モノマーを除去したポリマ
ー100部蚤こ、n−ブチルスズオキサイド0.6部を
加え、ポリエチレン板上で深さ3朋の型の中に流し込み
、20℃、65チ□RHの室内で7日間放置したところ
、半透明なシート状硬化物が得られる。このシートをJ
IS K−6301に規定の3号ダンベルと東洋精機
社製ストログラフを用い、JIS K−6301の規
定に従って300+++m/分の引張り速度で測定した
ところ、伸び率800〜850%、切断強さ8.5〜9
.31であった。なお、硬化後の動的粘弾性測定(−1
00℃〜150℃の温度)の結果より硬1ヒ物が架橋ポ
リマーであることは確かである。これはテレケリツクの
一つの証明になるものと考えられる。Next, 100 parts of the polymer from which residual monomers had been removed by vacuum drying were added, and 0.6 parts of n-butyltin oxide was added, poured into a mold with a depth of 3 mm on a polyethylene plate, and heated at 20°C to a mold of 65 cm. When left in a RH room for 7 days, a translucent sheet-like cured product was obtained. This sheet
When measured using a No. 3 dumbbell specified in IS K-6301 and a strograph manufactured by Toyo Seiki Co., Ltd. at a tensile speed of 300+++ m/min according to the specifications of JIS K-6301, the elongation rate was 800 to 850%, and the breaking strength was 8. 5-9
.. It was 31. In addition, dynamic viscoelasticity measurement after curing (-1
00°C to 150°C), it is certain that the hard material is a crosslinked polymer. This is considered to be one proof of telekeritsuk.
実施例2
アクリル酸ブチル64gおよびビス(トリメトキシシリ
ルプロピル)ジスルフィド2.1gを硬質ガラス製重合
封管に仕込み、これを窒素置換膜気後溶封する。15〜
20℃の水槽中、約3印の距離から実施例1と同様の光
源でUVを照射しながら光重合を行う。16時間後、液
状ポリマーを取り出し、110℃で4時間の減圧重量変
化法番こよる重合収率を測定したところ、94.3%で
あった。Example 2 64 g of butyl acrylate and 2.1 g of bis(trimethoxysilylpropyl) disulfide are charged into a hard glass polymer sealing tube, which is then heat-sealed with a nitrogen-substituted film. 15~
Photopolymerization is carried out in a water tank at 20° C. while irradiating with UV from a distance of about 3 marks using the same light source as in Example 1. After 16 hours, the liquid polymer was taken out and the polymerization yield was measured at 110° C. for 4 hours under reduced pressure and weight change method, and it was found to be 94.3%.
このポリマーを用い、実施例1と同様にして硬化シート
を調製したところ、ゴム状弾性を示す硬化シートが得ら
れる。この硬化シートについて実施例1と同様番こゴム
物性を測定したところ、伸び率400〜500チ、切断
強さ10.1〜12.3 K9/dであった。When a cured sheet was prepared using this polymer in the same manner as in Example 1, a cured sheet exhibiting rubber-like elasticity was obtained. The physical properties of this cured sheet were measured in the same manner as in Example 1, and the elongation was 400 to 500 inches, and the cutting strength was 10.1 to 12.3 K9/d.
実施例3
メタクリル酸メチル50ダ、アクリル酸ブチル100g
、メチルジメトキシシリルプロピルメタクリレート1g
、ビス(メチルジメトキシシリルプロピル)ジスルフィ
ド3.5gおよびトルエン50gを用い、実施例1と同
様1こして光重合を行って透明で粘稠なポリマー溶液を
得る。重量変化法≦こよる重合収率は85%であった(
但し、トルエンは完全に気散するものとして計算する)
。Example 3 Methyl methacrylate 50 da, butyl acrylate 100 g
, 1g of methyldimethoxysilylpropyl methacrylate
Using 3.5 g of bis(methyldimethoxysilylpropyl) disulfide and 50 g of toluene, photopolymerization is carried out in the same manner as in Example 1 to obtain a transparent and viscous polymer solution. The polymerization yield according to the weight change method ≦ was 85% (
However, toluene is calculated assuming that it is completely diffused.)
.
このポリマー溶液100部にn−ブチルスズオキサイド
0.6部を加え、これをポリエチレン板上に厚み約0.
1朋で塗布し、20℃、65%RHの室内で7日間放置
硬化させたところ、透明なフィルムが得られる。このフ
ィルムをJISK−6301に規定の3号ダンベルと東
洋精機社製ストログラフを用い、JIS K−630
1の規定に従って300+u+/分の引張り速度で測定
したところ、伸び率300%、切断強さ30〜50即/
alであった。Add 0.6 parts of n-butyltin oxide to 100 parts of this polymer solution, and spread it on a polyethylene plate to a thickness of about 0.6 parts.
A transparent film was obtained by applying one coat and leaving it to cure in a room at 20° C. and 65% RH for 7 days. Using a No. 3 dumbbell specified in JIS K-6301 and a strograph manufactured by Toyo Seiki Co., Ltd., this film was processed according to JIS K-630.
When measured at a tensile rate of 300+u+/min according to the provisions of 1, the elongation rate was 300% and the cutting strength was 30-50/min.
It was al.
実施例4〜6
下記表1に示す配合のモノマーおよびジスルフィドを用
いる以外は、実施例3と同様にして、光重合を行ってポ
リマー溶液を得、その重合収率を測定し、さらにフィル
ムを作成してダンベルシート物性(伸び率、切断強さ)
を測定する。結果を表1に示す。Examples 4 to 6 Photopolymerization was performed to obtain a polymer solution in the same manner as in Example 3, except that the monomers and disulfide having the composition shown in Table 1 below were used, the polymerization yield was measured, and a film was further created. Physical properties of dumbbell sheet (elongation rate, cutting strength)
Measure. The results are shown in Table 1.
表 1
力 表中、各種略語または商品名の内容は以下の通りで
ある。Table 1 Power The contents of various abbreviations or product names in the table are as follows.
MMA :メタクリル酸メチル
2EHAニアクリル酸2−エチルヘキシルBAニアクリ
ル酸ブチル
S【:スチレン
KBM−502:信越化学工業昧製のr−メタアクリロ
キシシリルプロピルメチルジメトキシシラン
DMDS :ビス(メチルジメトキシシリルプロピル)
ジスルフィドMMA: Methyl methacrylate 2EHA 2-ethylhexyl diacrylate BA Butyl diacrylate S [: Styrene KBM-502: r-methacryloxysilylpropylmethyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. DMDS: Bis(methyldimethoxysilylpropyl)
disulfide
Claims (1)
素数1〜4のアルキル、R^3は炭素数1〜4のアルキ
レン、nは0〜2の整数、 Zは▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼ および▲数式、化学式、表等があります▼(R^4は水
素またはメチル、Y^1は炭素数2〜11のエステル基
、フェニルまたはハロゲン、Y^2は炭素数2〜6のエ
ステル基またはハロゲン、およびY^3は弗素または塩
素)の少なくとも1つで構成され、mは10〜1000
0である〕 で示されることを特徴とする分子両末端にアルコキシシ
リル基を有するビニルポリマー。 2、式: ▲数式、化学式、表等があります▼ 〔式中、R^1およびR^2は同一もしくは異なつて炭
素数1〜4のアルキル、R^3は炭素数1〜4のアルキ
レン、およびnは0〜2の整数である〕で示されるジス
ルフィド化合物の1種または2種以上と、式: ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ または ▲数式、化学式、表等があります▼ 〔式中、R^4は水素またはメチル、Y^1は炭素数2
〜11のエステル基、フェニルまたはハロゲン、Y^2
は炭素数2〜6のエステル基またはハロゲン、およびY
^3は弗素または塩素である〕で示されるビニル系モノ
マーの1種または2種以上とを光重合反応させることを
特徴とする、式:▲数式、化学式、表等があります▼ 〔式中、R^1、R^2、R^3およびnは前記と同意
義。 Zは▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼ および▲数式、化学式、表等があります▼(R^4、Y
^1、Y^2およびY^3は前記と同意義)の少なくと
も1つで構成され、mは10〜10000である〕 で示される分子両末端にアルコキシシリル基を有するビ
ニルポリマーの製法。 3、ビニル系モノマー以外にアルコキシシリル基を有す
るモノマーをも光重合反応に供する前記第2項記載の製
法。[Claims] 1. Formulas: ▲ Numerical formulas, chemical formulas, tables, etc. Alkylene from 1 to 4, n is an integer from 0 to 2, Z is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R ^4 is hydrogen or methyl, Y^1 is an ester group with 2 to 11 carbon atoms, phenyl or halogen, Y^2 is an ester group with 2 to 6 carbon atoms or halogen, and Y^3 is fluorine or chlorine). Consists of one piece, m is 10 to 1000
0] A vinyl polymer having alkoxysilyl groups at both ends of the molecule. 2. Formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are the same or different and are alkyl having 1 to 4 carbon atoms, R^3 is alkylene having 1 to 4 carbon atoms, and n is an integer from 0 to 2] and the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^4 is hydrogen or methyl, Y^1 is the number of carbon atoms 2
~11 ester groups, phenyl or halogen, Y^2
is an ester group having 2 to 6 carbon atoms or a halogen, and Y
Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3 and n have the same meanings as above. Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^4, Y
^1, Y^2, and Y^3 have the same meanings as above), and m is 10 to 10,000.] A method for producing a vinyl polymer having alkoxysilyl groups at both ends of the molecule. 3. The method according to item 2 above, wherein a monomer having an alkoxysilyl group in addition to the vinyl monomer is also subjected to the photopolymerization reaction.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21166785A JPH0753773B2 (en) | 1985-09-24 | 1985-09-24 | Telechelic vinyl polymer having alkoxysilyl group and process for producing the same |
EP86112415A EP0217178A3 (en) | 1985-09-24 | 1986-09-08 | Process for the production of telechelic vinyl polymer having alkoxysilyl group. |
US07/327,396 US4981937A (en) | 1985-09-24 | 1989-03-22 | Telechelic vinyl polymer having alkoxysilyl group |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21166785A JPH0753773B2 (en) | 1985-09-24 | 1985-09-24 | Telechelic vinyl polymer having alkoxysilyl group and process for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6270405A true JPS6270405A (en) | 1987-03-31 |
JPH0753773B2 JPH0753773B2 (en) | 1995-06-07 |
Family
ID=16609599
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21166785A Expired - Fee Related JPH0753773B2 (en) | 1985-09-24 | 1985-09-24 | Telechelic vinyl polymer having alkoxysilyl group and process for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0753773B2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988007554A1 (en) * | 1987-03-31 | 1988-10-06 | Sunstar Giken Kabushiki Kaisha | Telechelic low molecular weight vinyl resins having alkoxysilyl groups and process for their preparation |
JP2003183323A (en) * | 2001-07-20 | 2003-07-03 | Rohm & Haas Co | Polymer containing silicone ester and composition therefrom |
US7601781B2 (en) | 1998-10-08 | 2009-10-13 | Kaneka Corporation | Curable compositions |
US8067520B2 (en) | 2005-01-11 | 2011-11-29 | Kaneka Corporation | Curable composition |
WO2011152002A1 (en) | 2010-06-03 | 2011-12-08 | 株式会社カネカ | Moisture-curing reactive hot melt adhesive composition |
WO2012033030A1 (en) | 2010-09-09 | 2012-03-15 | 株式会社カネカ | Moisture-curable reactive hot-melt adhesive agent composition |
WO2012117902A1 (en) | 2011-03-02 | 2012-09-07 | 株式会社カネカ | Curable composition |
KR20170052491A (en) * | 2015-11-04 | 2017-05-12 | 린텍 가부시키가이샤 | Solventless adhesive composition, adhesive, adhesive sheet, and display |
-
1985
- 1985-09-24 JP JP21166785A patent/JPH0753773B2/en not_active Expired - Fee Related
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988007554A1 (en) * | 1987-03-31 | 1988-10-06 | Sunstar Giken Kabushiki Kaisha | Telechelic low molecular weight vinyl resins having alkoxysilyl groups and process for their preparation |
US7601781B2 (en) | 1998-10-08 | 2009-10-13 | Kaneka Corporation | Curable compositions |
JP2003183323A (en) * | 2001-07-20 | 2003-07-03 | Rohm & Haas Co | Polymer containing silicone ester and composition therefrom |
US8067520B2 (en) | 2005-01-11 | 2011-11-29 | Kaneka Corporation | Curable composition |
WO2011152002A1 (en) | 2010-06-03 | 2011-12-08 | 株式会社カネカ | Moisture-curing reactive hot melt adhesive composition |
WO2012033030A1 (en) | 2010-09-09 | 2012-03-15 | 株式会社カネカ | Moisture-curable reactive hot-melt adhesive agent composition |
WO2012117902A1 (en) | 2011-03-02 | 2012-09-07 | 株式会社カネカ | Curable composition |
KR20170052491A (en) * | 2015-11-04 | 2017-05-12 | 린텍 가부시키가이샤 | Solventless adhesive composition, adhesive, adhesive sheet, and display |
JP2017088663A (en) * | 2015-11-04 | 2017-05-25 | リンテック株式会社 | Solventless type adhesive composition, adhesive, adhesive sheet and display body |
CN106967380B (en) * | 2015-11-04 | 2020-12-22 | 琳得科株式会社 | Solvent-free adhesive composition, adhesive sheet, and display |
Also Published As
Publication number | Publication date |
---|---|
JPH0753773B2 (en) | 1995-06-07 |
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