JP4437606B2 - Compatibilizer - Google Patents

Description

【０００９】
［式中、
Ｘ：水素原子、置換基を有していてもよい平均炭素数１〜４２の１価の炭化水素基、カルボキシル基又はエステル基を示す。
Ｙ：置換基を有していてもよい平均炭素数１〜４２の１価の炭化水素基、カルボキシル基、エステル基、又は式−（ＡＯ）_m−Ｒ¹で表される基を示す。ここでＲ¹は置換基を有していてもよい平均炭素数１〜２８の１価の炭化水素基、平均炭素数１〜２２のフルオロアルキル基、平均炭素数６〜２４のフルオロアリール基、又は平均珪素原子数１〜５０のシロキシシリルプロピル基、Ａは平均炭素数１〜３のアルキレン基、ｍは１〜３０の数を示し、ｍ個のＡは同一でも異なっていても良い。またＸとＹは一緒になって環を形成していても良い。］
【００１０】
【発明実施の形態】
［相溶化剤］
本発明の相溶化剤の重合単位（Ｉ）において、Ｘ又はＹが１価の炭化水素基である場合、好ましい例として、平均炭素数１〜２２のアルキル基もしくはアルケニル基、平均炭素数６〜１４のアリール基、又は平均炭素数７〜１８のアリールアルキル基もしくはアルキルアリール基が挙げられる。さらに好ましい例として、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、オクチル基、デシル基、ドデシル基、セチル基、ステアリル基、フェニル基、フェネチル基、ブチルフェニル基、ノニルフェニル基等が挙げられる。また、ＸとＹは一緒になって環を形成していても良く、この場合ＸとＹは、―（ＣＨ₂）_s−で表される連結基であることが好ましく、ｓは好ましくは３〜６の整数、更に好ましくは４である。
【００１１】
上記炭化水素基は置換基を有していてもよいが、その置換基として、ヒドロキシ基、平均炭素数が１〜２２のアルコキシ基、アミノ基、ジメチルアミノ基、ジエチルアミノ基、平均炭素数１〜１８のアミド基、平均炭素数１〜１８のアルキルアンモニウム基、アンモニウム基、メチルエステル基、エチルエステル基、フェニルエステル基、平均炭素数１〜１８のアシル基、シリル基、ＦやＣｌ等のハロゲン原子（以下、「本発明の置換基」という）等が挙げられる。
【００１２】
Ｘ又はＹはカルボキシル基であってもよいが、この場合、一般式（Ｉ）中の一部又は全てのカルボキシル基が、リチウム、ナトリウム、カリウム、アンモニウム等のカチオン種の１種又は２種以上と塩形成していてもよい。これらの中ではナトリウム又はアンモニウム塩が好ましい。
【００１３】
Ｘ又はＹはエステル基であってもよいが、好ましい例として、メチルエステル、エチルエステル、プロピルエステル、ブチルエステル、オクチルエステル、フェニルエステル、アリルエステル等が例示できる。
【００１４】
重合単位（Ｉ）において、Ｙは式−（ＡＯ）_m−Ｒ¹［式中、Ａ、ｍ、Ｒ¹は前記の意味を示す。］で表される基であってもよいが、Ａとして、メチレン基、エチレン基又はプロピレン基が例示され、ｍは好ましくは１〜２０、さらに好ましくは１又は５〜１０の数である。またｍ個のＡは同一でも異なっていても良い。Ａとｍの組合せとしては、Ａがメチレン基でｍが１である組合せが特に好ましい。
【００１５】
またＲ¹が炭化水素基である場合、好ましい例として、平均炭素数１〜２０のアルキル基もしくはアルケニル基、平均炭素数６〜１４のアリール基、又は平均炭素数７〜１８のアリールアルキル基もしくはアルキルアリール基が挙げられる。さらに好ましい例として、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、オクチル基、デシル基、ドデシル基、セチル基、ステアリル基、フェニル基、ノニルフェニル基等が挙げられる。Ｒ¹がフルオロアルキル基である場合、好ましい例として、１Ｈ，１Ｈ，２Ｈ，２Ｈ−ノナフルオロヘキシル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ −トリデカフルオロオクチル基、１Ｈ，１Ｈ，２Ｈ，２Ｈ −ヘプタデカフルオロデシル基、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル基、１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプチル基、１Ｈ，１Ｈ，９Ｈ−ヘキサデカフルオロノニル基等が挙げられる。Ｒ¹がフルオロアリール基である場合、好ましい例として、パーフルオロフェニル基が挙げられる。Ｒ¹がシロキシシリルプロピル基である場合、好ましくは珪素原子数１〜３０、さらに好ましくは１〜２０の直鎖又は分岐鎖のシロキシシリルプロピル基が挙げられる。これらシロキシシリルプロピル基の珪素原子に結合するアルキル置換基は、同一又は異なっていてもよく、メチル基、ブチル基、ビニル基、フェニル基等が例示できる。Ｒ¹は置換基を有していてもよいが、その置換基として、前記「本発明の置換基」が挙げられる。
【００１６】
重合単位（Ｉ）を与えるモノマーとしては、式(II)
【００１７】
【化３】

【００１８】
（式中、Ｒ¹は前記の意味を示す。）
で表されるグリシジルエーテル、エピハロヒドリン等が挙げられる。
【００１９】
本発明の相溶化剤において、重合単位（Ｉ）を有するポリエーテルは、Ｘ及びＹで示される基がそれぞれ異なる複数の重合単位を有するものであってもよく、その場合、ポリエーテル主鎖におけるそれらの重合単位の配列様式は、ブロック、交互、周期、統計（ランダムを含む）の何れであってもよい。
【００２０】
また本発明の相溶化剤は、重合単位（Ｉ）のみからなるポリエーテルだけでなく、他の重合単位とのコポリマーであっても良い。この場合、他の重合単位に特に制限はないが、本発明の相溶化剤で相溶化の大幅改善を図ろうとする重合体群の内のひとつに対して、相溶性の高い重合単位が好ましい。重合単位（Ｉ）と、他の重合単位（複数種であってもよい）との配列様式は、ブロック、交互、周期、統計（ランダムを含む）、グラフトの何れであってもよい。
【００２１】
本発明の相溶化剤が上記のようなコポリマーである場合、コポリマー中における重合単位（Ｉ）のモル分率は、好ましくは０．１以上１．０未満であり、さらに好ましくは０．３以上１．０未満、特に好ましくは０．５以上１．０未満である。
【００２２】
本発明の相溶化剤において、重合鎖の末端基に特に制限はない。合成法により特に末端基を制御できる場合、好ましい末端基として、水素原子、ハロゲン原子、ヒドロキシ基、平均炭素数１〜２２のアルキル基又はアルコキシ基、アミノ基、ジメチルアミノ基、ジエチルアミノ基、平均炭素数１〜１８のアミド基、平均炭素数１〜１８のアシル基、メチルエステル基、エチルエステル基、カルボキシル基等が例示される。
【００２３】
本発明の相溶化剤の分子量は、好ましくは１０００〜２００，０００，０００、さらに好ましくは１０，０００〜１００，０００，０００、特に好ましくは、３０，０００〜５０，０００，０００である。
【００２４】
［重合体］
本発明の重合体組成物に配合されうる重合体は特に制限はなく、既存の各種の合成樹脂やゴム類等を用いることができる。本発明で用いることのできる合成樹脂として、ポリオレフィン（ポリエチレン、ポリプロピレン等）、ポリスチレン、ポリメチルメタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル、ポリカーボネート、ＡＢＳ樹脂、ＡＳ樹脂、ＡＥＳ樹脂、ポリアミド６、ポリアミド６６、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリフェニレンオキシド、ポリテトラフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン−エチレン共重合体、ポリ（ビニリデンフルオリド）、ポリジメチルシリコーン、ポリジフェニルシリコーン、ワックス等の熱可塑性樹脂及びそれらの誘導体、並びにそれらを含む共重合体や、エポキシ樹脂、フェノール樹脂、ポリイミド、ポリウレタン、メラミン樹脂、ウレア樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂及びそれらの誘導体が例示される。
【００２５】
本発明で用いることのできるゴムとして、天然ゴム、ブタジエンゴム、スチレン−ブタジエンゴム、イソプレンゴム、ブチルゴム、エチレン−プロピレン共重合体、エチレン−プロピレン−ジエン共重合体、ニトリル−ブタジエンゴム、クロロプレンゴム、ウレタンゴム、エピクロロヒドリンゴム、シリコーンゴム、熱可塑性エラストマー等が例示される。
これらの中で、ポリオレフィン、ＡＢＳ樹脂、ゴムが好ましく用いられる。
【００２６】
［重合体組成物とその製造法］
本発明の相溶化剤は、特定の組み合わせの重合体に限定されることなく、広範な種類の重合体相互の相溶性を大幅に改善することができる。２種以上の重合体と本発明の相溶化剤を含有した重合体組成物は、優れた物性のポリマーブレンドを得る上で有用である。
【００２７】
本発明の相溶化剤は、極めて少量の添加量でも、相互に相溶性の低い２種以上の重合体を相溶化できる。本発明の相溶化剤の使用量は、相溶性を改善しようとする重合体の種類や組成比、実現したい重合体組成物の物性並びにモルフォロジー等によって決定されるが、概ね、重合体の総量１００重量部に対し、０．０５〜３０重量部が好ましく、より好ましくは０．１〜１５重量部、特に好ましくは０．５〜１０重量部である。
【００２８】
本発明の相溶化剤を混合して、本発明の重合体組成物を得るに際して、相溶性を改善しようとする重合体群の全てが熱可塑性である場合、これらを一軸押出機、二軸押出機、ロール混練機、バンバリーミキサー、ブラベンダー等を用いる既存の方法で２種以上の重合体を溶融混練する際に本発明の相溶化剤を混合すればよい。また、相溶性を改善しようとする重合体群に熱硬化性樹脂が含まれる場合は、熱硬化性樹脂前駆体の段階で２種以上の重合体と本発明の相溶化剤を含む他の成分とを上記のような既存の方法で混合した後、硬化させることができる。相溶性を改善しようとする重合体群にゴムが含まれる場合、上記のような方法で２種以上の重合体と本発明の相溶化剤を混合して重合体組成物を得た後に架橋することができる。
【００２９】
これらの２種以上の重合体と本発明の相溶化剤を混合する際に、添加順序に制限は無く、２種以上の重合体に相溶化剤を添加してもよく、相溶化剤に２種以上重合体を添加してもよく、又は１種以上の重合体に相溶化剤を添加した後、さらに１種以上の重合体を添加してもよい。
【００３０】
本発明の重合体組成物は、その相溶性に重大な影響を与えない限りにおいて、酸化防止剤、老化防止剤又はその他の安定剤、防腐剤、粘度調整剤、難燃剤や、分散剤、界面活性剤等の添加剤や、顔料、各種フィラー等を併用することができる。
【００３１】
［相溶性］
本発明の相溶化剤は、２種以上の重合体に配合することにより、樹脂強度（引張り弾性率、破断強度）を向上させることができる。
【００３２】
【実施例】
実施例及び比較例には、以下に示す本発明の相溶化剤Ａ〜Ｃ及び比較相溶化剤Ｄを用い、これらの数平均分子量（以下、Ｍｎと略記）はＧＰＣ分析により測定し、測定にはウォーターズ社製１５０Ｃ型を使用し、カラムは昭和電工社製Ｓｈｏｄｅｘ HT-806、Ｓｈｏｄｅｘ HT-803（×２本）を用いた（１３０℃、ｏ−ジクロロベンゼン、ポリスチレン換算分子量）。
【００３３】
また重合体組成物の動的粘弾性測定、熱変形温度測定並びに貯蔵弾性率測定には、アイティー計測制御社製ＤＶＡ―２２５を使用し、引張り弾性率と破断強度の測定には、ＯＲＩＥＮＴＥＣ社製ＴＥＮＳＩＬＯＮ ＵＣＴ−１００を使用した。また、アイゾット強度の測定は、ＪＩＳ規格に準じて行った。
【００３４】
＜相溶化剤＞
相溶化剤Ａ
ポリ（セチルグリシジルエーテル）；一般式（Ｉ）において、Ｘ＝Ｈ、Ｙ＝−（ＡＯ）_m―Ｒ¹で、Ａ＝メチレン基、ｍ＝１、Ｒ¹＝―（ＣＨ₂）₁₅ＣＨ₃、Ｍｎ＝３３万。
【００３５】
相溶化剤Ｂ
２−エチルヘキシルグリシジルエーテル−エピクロロヒドリン共重合体（８０：２０）；一般式（Ｉ）において、Ｘ＝Ｈ、Ｙ＝−（ＡＯ）_m―Ｒ¹で、Ａ＝メチレン基、ｍ＝１、Ｒ¹＝２−エチルヘキシル基である重合単位と、一般式（Ｉ）において、Ｘ＝Ｈ、Ｙ＝−ＣＨ₂Ｃｌである重合単位の８０：２０ランダム共重合体、Ｍｎ＝２５万。
【００３６】
相溶化剤Ｃ
ドデシルグリシジルエーテル−ブタジエン共重合体（７０：３０）；一般式（Ｉ）において、Ｘ＝Ｈ、Ｙ＝−（ＡＯ）_m―Ｒ¹で、Ａ＝メチレン基、ｍ＝１、Ｒ¹＝―（ＣＨ₂）₁₁ＣＨ₃である重合単位と、ブタジエンの７０：３０ブロック共重合体、Ｍｎ＝３万。
【００３７】
比較相溶化剤Ｄ
エチレン−メチルメタクリレートグラフト共重合体（９０：１０）、Ｍｎ＝９千。
【００３８】
実施例１
ポリプロピレン樹脂９０重量部とポリメチルメタクリレート１０重量部を二軸押出し機で２１０℃にて混練するに際し、相溶化剤Ａ ０．４重量部を添加し、ポリプロピレン／ポリメチルメタクリレート組成物を得た。
【００３９】
比較例１−１
相溶化剤Ａを添加しなかった以外は実施例１と同様にして、ポリプロピレン／ポリメチルメタクリレート組成物を得た。
【００４０】
比較例１−２
相溶化剤Ａの代わりに比較相溶化剤Ｄ ２重量部を添加した以外は実施例１と同様にして、ポリプロピレン／ポリメチルメタクリレート組成物を得た。
【００４１】
実施例１、比較例１−１及び比較例１−２で得たポリプロピレン／ポリメチルメタクリレート組成物のアイゾット強度、引っ張り弾性率、破断強度を測定した。結果を表１に示す。
【００４２】
【表１】

【００４３】
参考例２
ポリプロピレン８０重量部とポリ塩化ビニル２０重量部を１８０℃にて二軸押し出し機で混練するに際し、相溶化剤Ｂ ０．４重量部を添加し、ポリプロピレン／ポリ塩化ビニル組成物を得た。
【００４４】
比較例２
相溶化剤Ｂを添加しなかった以外は、参考例２と同様にして、ポリプロピレン／ポリ塩化ビニル組成物を得た。
【００４５】
参考例２及び比較例２で得た、ポリプロピレン／ポリ塩化ビニル組成物のアイゾット強度と破断強度を測定した。結果を表２に示す。
【００４６】
【表２】

【００４７】
参考例３
天然ゴム５０重量部とスチレン−ブタジエンゴム５０重量部を１４０℃にてバンバリーミキサーで１０分間混練するに際し、相溶化剤Ｃ １重量部を添加した。得られた天然ゴム／スチレン−ブタジエンゴム組成物１００重量部に、硫黄１．５重量部、加硫促進剤（ＤＭ）２部、加硫促進剤（ＮＢＳ）２部、ステアリン酸亜鉛１．５部、 酸化亜鉛１部を加えて、７０℃にて７分間ロール混練した後、１７０℃で１０分間プレス架橋して、天然ゴム／スチレン−ブタジエンゴム架橋組成物を得た。
【００４８】
比較例３
相溶化剤Ｃを添加しなかった以外は、参考例３と同様にして、天然ゴム／スチレン−ブタジエンゴム架橋組成物を得た。
【００４９】
参考例３及び比較例３で得た、天然ゴム／スチレン−ブタジエンゴム架橋組成物の貯蔵弾性率、ｔａｎδ値、破断強度を測定した。結果を表３に示す。
【００５０】
【表３】

【００５１】
【発明の効果】
本発明の相溶化剤は、特定の組み合わせの重合体に限定されることなく、広範な種類の重合体相互の相溶性を大幅に改善し、優れた強度物性を有するポリマーブレンドを得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a compatibilizing agent effective for improving the compatibility of different polymers, a polymer composition containing the compatibilizing agent, and a method for producing the same.
[0002]
[Prior art and problems to be solved by the invention]
The so-called polymer blending technique, in which different polymers are mixed to obtain a polymer material with improved physical properties such as mechanical strength, heat resistance, weather resistance, chemical resistance, fluidity, and moldability, It has attracted much attention in recent years because it is faster and more economical than the development of new polymer materials. In general, blends of high molecular weight polymers are extremely disadvantageous thermodynamically compared to the case of low molecular weight compounds, and are easily incompatible even if their chemical structures are close. This is because among the elements constituting the free energy of mixing, the entropy term (negative) has a small absolute value when the component is of high molecular weight, while the enthalpy term takes a large positive value associated with the χ parameter. Because.
[0003]
Various compatibilizers have been developed for blending dissimilar polymers that are essentially immiscible. The basic compatibilizer used so far has been to use block copolymers or graft copolymers containing both polymer components. However, in the synthesis, it is necessary to adopt a special polymerization method that can strictly control the chain length of both components, such as a living polymerization method, and it is expensive, and the combination of applicable polymers is extremely limited. Had the disadvantage of being.
[0004]
In addition, a functional group rich in reactivity such as acid anhydride, carboxylic acid, epoxide, etc. is introduced into a part of one polymer, and this is heated / mixed with another polymer component capable of reacting with this functional group. There is also a method of obtaining a polymer blend by grafting or blocking with a polymer to obtain a polymer blend. In this method, a polypropylene / nylon blend composition, an ethylene-propylene-diene copolymer / nylon blend composition, a polypropylene / polyethylene terephthalate is actually used. A blend composition or the like is obtained. However, this method can be applied only to a combination of polymer components in which one is inactive to the functional group and the other is active, and a reactive polymer usually reacts only at the end of the polymer chain, so the reaction efficiency is extremely high. There has been a problem that a high molecular weight polymer having a low terminal density does not function sufficiently.
[0005]
Furthermore, none of these existing compatibilizers are still satisfactory in their compatibilizing ability. The degree of compatibilization between different polymers can be estimated simply by the particle size of the dispersed phase after kneading under a certain share, and it can be said that the more finely dispersed, the higher the compatibility. Further, since the interface between different polymers having a large interfacial tension and lacking affinity is easily peeled off, the impact resistance of conventional polymer blends often showed a remarkably low value. More quantitatively, the affinity of the interface can be evaluated by measuring the dynamic viscoelasticity of the polymer composition. That is, it can be said that the smaller the tan δ value indicating the energy loss with respect to cycle stimulation, the stronger the interface is formed without interfacial peeling or mismatching, but the tan δ value of the polymer blend obtained using the conventional compatibilizing agent Was extremely large.
[0006]
An object of the present invention is to provide a non-reactive compatibilizing agent that improves the compatibilization of two or more polymers having low compatibility with each other, a polymer composition containing the compatibilizing agent, and a method for producing the same. .
[0007]
[Means for Solving the Problems]
The present invention relates to a compatibilizer comprising a polyether having a polymer unit represented by general formula (I) (hereinafter referred to as polymer unit (I)), and a polymer containing the compatibilizer and two or more polymers. A composition, a polymer composition containing the polyether and two or more polymers, and a method for producing these polymer compositions are provided.
[0008]
[Chemical formula 2]

[0009]
[Where:
X: A hydrogen atom, a monovalent hydrocarbon group having 1 to 42 carbon atoms which may have a substituent, a carboxyl group or an ester group.
Y: A monovalent hydrocarbon group having 1 to 42 average carbon atoms, a carboxyl group, an ester group, or a group represented by the formula — (AO) _m —R ^1, which may have a substituent. Here, R ¹ may have a substituent, a monovalent hydrocarbon group having 1 to 28 average carbon atoms, a fluoroalkyl group having 1 to 22 average carbon atoms, a fluoroaryl group having 6 to 24 average carbon atoms, Alternatively, a siloxysilylpropyl group having 1 to 50 average silicon atoms, A represents an alkylene group having 1 to 3 average carbon atoms, m represents a number of 1 to 30, and m A may be the same or different. X and Y may be combined to form a ring. ]
[0010]
DETAILED DESCRIPTION OF THE INVENTION
[Compatibilizer]
In the polymerization unit (I) of the compatibilizing agent of the present invention, when X or Y is a monovalent hydrocarbon group, preferred examples include an alkyl group or an alkenyl group having an average carbon number of 1 to 22, an average carbon number of 6 to 14 aryl groups, or an arylalkyl group or alkylaryl group having an average carbon number of 7-18. Further preferred examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, phenyl group, phenethyl group, A butylphenyl group, a nonylphenyl group, etc. are mentioned. X and Y may be combined to form a ring. In this case, X and Y are preferably a linking group represented by — (CH ₂ ) _s —, and s is preferably 3 An integer of ˜6, more preferably 4.
[0011]
The hydrocarbon group may have a substituent, and as the substituent, a hydroxy group, an alkoxy group having an average carbon number of 1 to 22, an amino group, a dimethylamino group, a diethylamino group, an average carbon number of 1 to 18 amide groups, alkyl ammonium groups having 1 to 18 carbon atoms, ammonium groups, methyl ester groups, ethyl ester groups, phenyl ester groups, acyl groups having 1 to 18 carbon atoms in average, silyl groups, halogens such as F and Cl Atom (hereinafter referred to as “substituent of the present invention”) and the like.
[0012]
X or Y may be a carboxyl group. In this case, one or more of the cation species such as lithium, sodium, potassium, ammonium, etc. may be used in some or all of the carboxyl groups in the general formula (I). And may form a salt. Of these, sodium or ammonium salts are preferred.
[0013]
X or Y may be an ester group, but preferred examples include methyl ester, ethyl ester, propyl ester, butyl ester, octyl ester, phenyl ester, allyl ester and the like.
[0014]
In the polymerization unit (I), Y represents the formula — (AO) _m —R ¹ , wherein A, m and R ¹ have the above-mentioned meanings. In the formula, A is exemplified by a methylene group, an ethylene group or a propylene group, and m is preferably a number of 1 to 20, more preferably 1 or 5 to 10. The m A's may be the same or different. As a combination of A and m, a combination in which A is a methylene group and m is 1 is particularly preferable.
[0015]
When R ¹ is a hydrocarbon group, preferred examples include an alkyl group or alkenyl group having an average carbon number of 1 to 20, an aryl group having an average carbon number of 6 to 14, or an arylalkyl group having an average carbon number of 7 to 18 or An alkylaryl group is mentioned. Further preferred examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, phenyl group, nonylphenyl group. Etc. When R ¹ is a fluoroalkyl group, preferred examples include 1H, 1H, 2H, 2H-nonafluorohexyl group, 1H, 1H, 2H, 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-hepta. Examples include a decafluorodecyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, 1H, 1H, 9H-hexadecafluorononyl group and the like. When R ¹ is a fluoroaryl group, a preferred example is a perfluorophenyl group. When R ¹ is a siloxysilylpropyl group, a linear or branched siloxysilylpropyl group having 1 to 30 silicon atoms, more preferably 1 to 20 is preferable. These alkyl substituents bonded to the silicon atom of the siloxysilylpropyl group may be the same or different, and examples thereof include a methyl group, a butyl group, a vinyl group, and a phenyl group. R ¹ may have a substituent, and examples of the substituent include the “substituent of the present invention”.
[0016]
Monomers that give polymerized units (I) include those of formula (II)
[0017]
[Chemical 3]

[0018]
(In the formula, R ¹ has the above-mentioned meaning.)
And glycidyl ether, epihalohydrin and the like.
[0019]
In the compatibilizing agent of the present invention, the polyether having the polymerized unit (I) may have a plurality of polymerized units having different groups represented by X and Y, and in that case, in the polyether main chain. The arrangement pattern of these polymerization units may be any of block, alternating, period, and statistics (including random).
[0020]
Further, the compatibilizing agent of the present invention may be not only a polyether composed only of the polymerized units (I) but also a copolymer with other polymerized units. In this case, the other polymerized units are not particularly limited, but polymerized units having high compatibility are preferred for one of the polymer groups for which the compatibilizing agent of the present invention is to greatly improve the compatibilization. The arrangement pattern of the polymerized unit (I) and other polymerized units (may be plural types) may be any of block, alternating, periodic, statistical (including random), and graft.
[0021]
When the compatibilizing agent of the present invention is a copolymer as described above, the molar fraction of polymerized units (I) in the copolymer is preferably 0.1 or more and less than 1.0, more preferably 0.3 or more. It is less than 1.0, particularly preferably 0.5 or more and less than 1.0.
[0022]
In the compatibilizing agent of the present invention, there is no particular limitation on the terminal group of the polymer chain. In the case where the terminal group can be controlled particularly by the synthesis method, the preferred terminal group includes a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group or alkoxy group having an average carbon number of 1 to 22, an amino group, a dimethylamino group, a diethylamino group, an average carbon Examples include an amide group having 1 to 18 carbon atoms, an acyl group having 1 to 18 carbon atoms in average, a methyl ester group, an ethyl ester group, and a carboxyl group.
[0023]
The molecular weight of the compatibilizer of the present invention is preferably 1000 to 200,000,000, more preferably 10,000 to 100,000,000, and particularly preferably 30,000 to 50,000,000.
[0024]
[Polymer]
The polymer that can be blended in the polymer composition of the present invention is not particularly limited, and various existing synthetic resins and rubbers can be used. Synthetic resins that can be used in the present invention include polyolefin (polyethylene, polypropylene, etc.), polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycarbonate, ABS resin, AS resin, AES resin, polyamide 6, polyamide 66, Polyetherimide, polyether ether ketone, polyphenylene oxide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-ethylene copolymer, poly (Vinylidene fluoride), polydimethyl silicone, polydiphenyl silicone, thermoplastic resins such as wax and derivatives thereof, and copolymers containing them Epoxy resins, phenolic resins, polyimide, polyurethane, melamine resins, urea resins, polyester resins, thermosetting resins and derivatives thereof and unsaturated polyester resins.
[0025]
As rubbers that can be used in the present invention, natural rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, butyl rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, nitrile-butadiene rubber, chloroprene rubber, Examples include urethane rubber, epichlorohydrin rubber, silicone rubber, thermoplastic elastomer and the like.
Among these, polyolefin, ABS resin, and rubber are preferably used.
[0026]
[Polymer composition and production method thereof]
The compatibilizing agent of the present invention is not limited to a specific combination of polymers, and can greatly improve the compatibility between a wide variety of polymers. A polymer composition containing two or more polymers and the compatibilizer of the present invention is useful for obtaining a polymer blend having excellent physical properties.
[0027]
The compatibilizing agent of the present invention can compatibilize two or more kinds of polymers having low compatibility with each other even with an extremely small addition amount. The amount of the compatibilizing agent of the present invention is determined by the type and composition ratio of the polymer to be improved in compatibility, the physical properties of the polymer composition to be realized, the morphology, etc. 0.05-30 weight part is preferable with respect to a weight part, More preferably, it is 0.1-15 weight part, Especially preferably, it is 0.5-10 weight part.
[0028]
When the compatibilizing agent of the present invention is mixed to obtain the polymer composition of the present invention, if all of the polymer groups whose compatibility is to be improved are thermoplastic, these are converted into a single-screw extruder, a twin-screw extruder, and the like. The compatibilizer of the present invention may be mixed when two or more kinds of polymers are melt-kneaded by an existing method using a machine, a roll kneader, a Banbury mixer, a Brabender, or the like. Further, when the thermosetting resin is contained in the polymer group to improve the compatibility, other components including two or more polymers and the compatibilizing agent of the present invention at the stage of the thermosetting resin precursor. Can be cured after mixing by the existing method as described above. When rubber is included in the polymer group whose compatibility is to be improved, two or more kinds of polymers and the compatibilizing agent of the present invention are mixed by the above-described method to obtain a polymer composition, followed by crosslinking. be able to.
[0029]
When mixing these two or more types of polymers and the compatibilizing agent of the present invention, there is no limitation on the order of addition, and the compatibilizing agent may be added to two or more types of polymers. One or more kinds of polymers may be added, or one or more kinds of polymers may be further added after adding a compatibilizing agent to one or more kinds of polymers.
[0030]
The polymer composition of the present invention has an antioxidant, an anti-aging agent or other stabilizer, an antiseptic, a viscosity modifier, a flame retardant, a dispersant, an interface, as long as the compatibility is not seriously affected. Additives such as activators, pigments, various fillers, and the like can be used in combination.
[0031]
[Compatibility]
The compatibilizing agent of the present invention can improve the resin strength (tensile modulus, breaking strength) by blending with two or more polymers.
[0032]
【Example】
In Examples and Comparative Examples, the following compatibilizers A to C and comparative compatibilizer D of the present invention are used, and their number average molecular weight (hereinafter abbreviated as Mn) is measured by GPC analysis. Waters 150C type was used, and Shodex HT-806 and Shodex HT-803 (× 2) made by Showa Denko Co., Ltd. were used (130 ° C., o-dichlorobenzene, polystyrene equivalent molecular weight).
[0033]
In addition, DVA-225 manufactured by IT Measurement & Control Co., Ltd. is used for dynamic viscoelasticity measurement, thermal deformation temperature measurement and storage elastic modulus measurement of the polymer composition, and ORIENTEC is used for measurement of tensile elastic modulus and breaking strength. TENSILON UCT-100 manufactured by the company was used. The Izod strength was measured according to JIS standards.
[0034]
<Compatibilizer>
Compatibilizer A
Poly (cetylglycidyl ether); in the general formula (I), X = H, Y =-(AO) _m -R ¹ , A = methylene group, m = 1, R ¹ =-(CH ₂ ) ₁₅ CH ₃ , Mn = 330,000.
[0035]
Compatibilizer B
2-ethylhexyl glycidyl ether-epichlorohydrin copolymer (80:20); in general formula (I), X = H, Y =-(AO) _m -R ¹ , A = methylene group, m = 1 80:20 random copolymer of polymer units in which R ¹ = 2-ethylhexyl group and polymer units in general formula (I) where X = H and Y = —CH ₂ Cl, Mn = 250,000.
[0036]
Compatibilizer C
Dodecyl glycidyl ether-butadiene copolymer (70:30); In general formula (I), X = H, Y =-(AO) _m -R ¹ , A = methylene group, m = 1, R ¹ =- (CH ₂ ) ₁₁ CH ₃ polymerized units and butadiene 70:30 block copolymer, Mn = 30,000.
[0037]
Comparative compatibilizer D
Ethylene-methyl methacrylate graft copolymer (90:10), Mn = 9000.
[0038]
Example 1
When kneading 90 parts by weight of polypropylene resin and 10 parts by weight of polymethyl methacrylate with a twin screw extruder at 210 ° C., 0.4 part by weight of compatibilizer A was added to obtain a polypropylene / polymethyl methacrylate composition.
[0039]
Comparative Example 1-1
A polypropylene / polymethyl methacrylate composition was obtained in the same manner as in Example 1 except that the compatibilizer A was not added.
[0040]
Comparative Example 1-2
A polypropylene / polymethyl methacrylate composition was obtained in the same manner as in Example 1 except that 2 parts by weight of the comparative compatibilizer D was added instead of the compatibilizer A.
[0041]
The Izod strength, tensile modulus, and breaking strength of the polypropylene / polymethyl methacrylate compositions obtained in Example 1, Comparative Example 1-1, and Comparative Example 1-2 were measured. The results are shown in Table 1.
[0042]
[Table 1]

[0043]
Reference example 2
When kneading 80 parts by weight of polypropylene and 20 parts by weight of polyvinyl chloride with a twin screw extruder at 180 ° C., 0.4 part by weight of compatibilizer B was added to obtain a polypropylene / polyvinyl chloride composition.
[0044]
Comparative Example 2
A polypropylene / polyvinyl chloride composition was obtained in the same manner as in Reference Example 2 except that the compatibilizer B was not added.
[0045]
The Izod strength and breaking strength of the polypropylene / polyvinyl chloride compositions obtained in Reference Example 2 and Comparative Example 2 were measured. The results are shown in Table 2.
[0046]
[Table 2]

[0047]
Reference example 3
When kneading 50 parts by weight of natural rubber and 50 parts by weight of styrene-butadiene rubber with a Banbury mixer at 140 ° C. for 10 minutes, 1 part by weight of compatibilizer C was added. To 100 parts by weight of the obtained natural rubber / styrene-butadiene rubber composition, 1.5 parts by weight of sulfur, 2 parts of vulcanization accelerator (DM), 2 parts of vulcanization accelerator (NBS), 1.5 parts of zinc stearate And 1 part of zinc oxide were added and roll kneaded at 70 ° C. for 7 minutes, followed by press crosslinking at 170 ° C. for 10 minutes to obtain a natural rubber / styrene-butadiene rubber crosslinked composition.
[0048]
Comparative Example 3
A natural rubber / styrene-butadiene rubber crosslinked composition was obtained in the same manner as in Reference Example 3 except that the compatibilizer C was not added.
[0049]
The storage elastic modulus, tan δ value, and breaking strength of the natural rubber / styrene-butadiene rubber crosslinked composition obtained in Reference Example 3 and Comparative Example 3 were measured. The results are shown in Table 3.
[0050]
[Table 3]

[0051]
【The invention's effect】
The compatibilizing agent of the present invention is not limited to a specific combination of polymers, and can greatly improve the compatibility between a wide variety of polymers to obtain a polymer blend having excellent strength properties. .

Claims (4)

A compatibilizing agent for a heterogeneous polymer comprising a polyether having only a polymerization unit represented by formula (I).

[Where:
X: a hydrogen atom.
Y : represents a group represented by the formula — (AO) _m —R ¹ . Wherein R ¹ is an alkyl group which has an average carbon number may be 1 to 28 which have a substituent, A is the average alkylene group having 1 to 3 carbon atoms, m is shows the number of 1. ] A polymer composition comprising two or more polymers and a compatibilizer according to claim 1 (0.05 to 30 parts by weight with respect to 100 parts by weight of the polymer ) . At least one polyolefin polymer, polymer composition of claim 2 Symbol placing an ABS resin or rubber.   The manufacturing method of the polymer composition which mixes 2 or more types of polymers, and the compatibilizer of Claim 1.