JP5005124B2 - Method for producing polymer, polymer and use thereof - Google Patents

Description

【００１０】
（式中、Ｒ¹ 〜Ｒ⁴ は水素原子又は炭素数１〜１２の炭化水素基を示す。）
〔６〕 モノマ−が一般式（２）で表されるビニルエ−テル化合物から選ばれた１種又は２種以上の化合物である上記〔１〕〜〔４〕のいずれかに記載の重合体の製造方法。
【００１１】
【化１２】

【００１２】
（式中、Ｒ⁵ 〜Ｒ⁷ はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ⁸ は炭素数１〜１０の二価の炭化水素基、Ｒ⁹ は炭素数１〜２０の炭化水素基、ｐはその平均値が０〜１０の数を示し、Ｒ⁵ 〜Ｒ⁹ は構成単位毎に同一でもそれぞれ異なっていてもよく、またＲ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。）
〔７〕 モノマ−が、一般式（２）で表されるビニルエ−テル化合物から選ばれた１種又は２種以上の化合物、及び一般式（１）で表される炭化水素系ビニル化合物から選ばれた１種又は２種以上の化合物である上記〔１〕〜〔４〕のいずれかに記載の重合体の製造方法。
【００１３】
【化１３】

【００１４】
（式中、Ｒ⁵ 〜Ｒ⁷ はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ⁸ は炭素数１〜１０の二価の炭化水素基、Ｒ⁹ は炭素数１〜２０の炭化水素基、ｐはその平均値が０〜１０の数を示し、Ｒ⁵ 〜Ｒ⁹ は構成単位毎に同一でもそれぞれ異なっていてもよく、またＲ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。）
【００１５】
【化１４】

【００１６】
（式中、Ｒ¹ 〜Ｒ⁴ は水素原子又は炭素数１〜１２の炭化水素基を示す。）
〔８〕 重合反応がカチオン重合反応である上記〔１〕〜〔７〕のいずれかに記載の重合体の製造方法。
〔９〕 重合体の重量平均分子量が３００〜５００００であり、重合体の分子量分布（〔重量平均分子量〕／〔数平均分子量〕）が２．５以下でである上記〔１〕〜〔８〕のいずれかに記載の重合体の製造方法。
【００１７】
〔１０〕 重合体の分子量分布曲線におけるピ−ク強度の最大値に該当する分子量の３倍以上の分子量を有する重合体の含有量が全重合体の１重量％以下である上記〔１〕〜〔９〕のいずれかに記載の重合体の製造方法。
〔１１〕 上記〔１〕〜〔１０〕のいずれかに記載の方法により重合し、次いで水素化する重合体の製造方法。
【００１８】
〔１２〕 重合体がビニルエ−テル化合物の重合体又は共重合体であって、重合体の重量平均分子量が３００〜５００００であり、かつ、分子量分布曲線のピ−ク強度の最大値に該当する分子量の３倍以上の分子量を有する重合体の含有量が全重合体の１重量％以下である重合体。
〔１３〕 上記〔１２〕に記載の重合体を水素化して得られる重合体。
【００１９】
〔１４〕 重合体の構成単位が一般式（３）で表され、又は重合体の構成単位が一般式（３）及び（４）で表され、その末端が一般式（５）又は（６）及び一般式（７）又は（８）で表される上記〔１３〕に記載の重合体。
【００２０】
【化１５】

【００２１】
（式中、Ｒ⁵ 〜Ｒ⁷ はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ⁸ は炭素数１〜１０の二価の炭化水素基、Ｒ⁹ は炭素数１〜２０の炭化水素基、ｐはその平均値が０〜１０の数を示し、Ｒ⁵ 〜Ｒ⁹ は構成単位毎に同一でもそれぞれ異なっていてもよく、またＲ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。）
【００２２】
【化１６】

【００２３】
（式中、Ｒ¹ 〜Ｒ⁴ は水素原子又は炭素数１〜１２の炭化水素基を示す。）
【００２４】
【化１７】

【００２５】
（式中、Ｒ⁵ 〜Ｒ⁹ 及びｐは前記一般式（３）と同じ）
【００２６】
【化１８】

【００２７】
（式中、Ｒ¹ 〜Ｒ⁴ は前記一般式（４）と同じ）
【００２８】
【化１９】

【００２９】
（式中、Ｒ⁵ 〜Ｒ⁹ 及びｐは前記一般式（３）と同じ）
【００３０】
【化２０】

【００３１】
（式中、Ｒ¹ 〜Ｒ⁴ は前記一般式（４）と同じ）
〔１５〕 上記〔１０〕又は〔１１〕に記載された製造方法によって製造された重合体又は、上記〔１２〕〜〔１４〕のいずれかに記載の重合体を主成分とする圧縮式冷凍機用潤滑油。
【００３２】
【発明の実施の形態】
〔重合体の製造方法〕
本発明の重合体の製造方法は、触媒の存在下、モノマ−を逐次供給しながら重合する重合方法において、連鎖移動剤を逐次供給することを特徴とする重合体の製造方法である。
【００３３】
連鎖移動剤を一時に供給するのではなく、逐次供給して重合すれば、重合体の分子量分布を制御し、分子量分布が狭い重合体が製造される効果がある。この方法は、ラジカル重合、イオン重合を問わず、また、塊状重合、溶液重合等のいずれの重合様式であっても適用できる。
この方法で製造される重合体の分子量は特に制限はないが、重量平均分子量がおよそ３００〜５００００，さらには３００〜１００００，特に３００〜５０００の重合体を製造する場合に好ましく、有効である。
【００３４】
ここでいう「連鎖移動剤」とは、広く連鎖移動機能を有する化合物をいい、例えば、ラジカル重合においてはエチルベンゼン、イソプロピルベンゼン、クロロホルム等が、アニオン重合においては水、アルコ−ル類等が、カチオン重合においては水、アルコ−ル類、アミン類等の化合物が例示できる。
この連鎖移動剤を「逐次供給する」とは、反応初期等に一時に供給するのではなく、重合反応期間中に分散して供給することをいう。
【００３５】
従って、分散して供給するかぎり、断続的に供給しても、連続的に供給しても良い。この場合、モノマ−供給期間（時間）に対する連鎖移動剤を供給する期間（時間）の割合が高い程、分子量分布を狭くする効果が顕著であり、その割合が、１／２以上であること、さらには３／４以上、特に１／１つまり、全期間供給することが好ましい。
【００３６】
特に好ましい態様は、モノマ−の供給量に概略比例して連鎖移動剤を供給する方法であり、その点で、モノマ−の全供給期間を通じて、連鎖移動剤を連続的に供給する方法が好ましい。
具体的には、モノマ−とは別に連鎖移動剤を反応系に単独で供給する方法や、連鎖移動剤をモノマ−と混合して、モノマ−との混合物とし供給する方法が挙げられる。
【００３７】
また、連鎖移動剤を単独で供給する場合、これを加熱・気化して気体状態で、反応系に供給することもできる。この場合、気化した連鎖移動剤を反応系の気相部分へ供給すると、連鎖移動剤が液界面から溶け込み、均一に反応部分に作用し、また気相部での過重合を防止できため、より分子量分布が狭い重合体を得られる場合がある。この気化した連鎖移動剤は、窒素ガス等の同伴ガスとともに供給することもできる。
【００３８】
なお、モノマ−を逐次供給することを前提にする本発明の重合方法は、反応性が高いモノマ−を重合する場合、モノマ−を反応初期に一時に供給することにより重合反応が暴走する等の危険を防止する効果もある。
本発明でいう「触媒」は、重合反応を促進する物質であって、狭義のいわゆる重合触媒と重合開始剤とを含む意味である。従って、触媒として、いわゆる重合触媒と重合開始剤のいずれか一方のみを使用する場合と、両者を併用する場合がある。なお、ここでいう、重合触媒には通常の有体の触媒のみでなく、光、熱、放射線等の無体のものをも含む概念である。
【００３９】
本発明の重合体の製造方法は、上記触媒の存在下、モノマ−を逐次供給しつつ、連鎖移動剤を逐次供給して、目的の重合体が得られる反応温度、反応圧力、反応時間重合させればよい。
本発明に用いるモノマ−は特に制限はなく、あらゆるモノマ−が対象である。
ビニル化合物について言えば、炭化水素系モノマ−、極性モノマ−及び環状モノマ−があり、炭化水素系モノマ−（炭化水素系ビニル化合物）の場合は、一般式（１）で表されるものが含まれる。
【００４０】
【化２１】

【００４１】
（式中、Ｒ¹ 〜Ｒ⁴ は水素原子又は炭素数１〜１２の炭化水素基を示す。）
前記一般式（１）の炭化水素基は、直鎖、分岐鎖の飽和又は不飽和炭化水素基、及び環状飽和炭化水素基、芳香族炭化水素基を含む。
前記一般式（１）で表される好適な炭化水素系ビニルモノマ−としては、例えば、エチレン、プロピレン、各種ブテン、各種ペンテン、各種ヘキセン、各種ヘプテン、各種オクテン、ジイソブチレン、トリイソブチレン、スチレン、各種アルキル置換スチレン等を挙げることができる。
【００４２】
次に、モノマ−がビニル化合物のうち、極性モノマ−であるビニルエ−テル化合物を重合する場合を例に本発明の製造方法をより具体的に説明する。
本発明に用いるビニルエ−テルモノマ−としては一般式（２）で表わされるものが挙げられる。
【００４３】
【化２２】

【００４４】
（式中、Ｒ⁵ 〜Ｒ⁷ はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ⁸ は炭素数１〜１０の二価の炭化水素基、Ｒ⁹ は炭素数１〜２０の炭化水素基、ｐはその平均値が０〜１０の数を示し、Ｒ⁵ 〜Ｒ⁹ は構成単位毎に同一でもそれぞれ異なっていてもよく、またＲ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。）
前記一般式（２）におけるＲ⁵ 〜Ｒ⁷ は、それぞれ水素原子又は炭素数１〜８、好ましくは１〜４の炭化水素基を示す。ここで炭化水素基とは、具体的にはメチル基，エチル基，ｎ−プロピル基，イソプロピル基，各種ブチル基，各種ペンチル基，各種ヘキシル基，各種ヘプチル基，各種オクチル基のアルキル基、シクロペンチル基，シクロヘキシル基，各種メチルシクロヘキシル基，各種エチルシクロヘキシル基，各種ジメチルシクロヘキシル基などのシクロアルキル基、フェニル基，各種メチルフェニル基，各種エチルフェニル基，各種ジメチルフェニル基のアリール基、ベンジル基，各種フェニルエチル基，各種メチルベンジル基のアリールアルキル基を挙げることができる。なお、これらのＲ⁵ 〜Ｒ⁷ としては、特に水素原子が好ましい。
【００４５】
一方、前記一般式（２）におけるＲ⁸ は、炭素数１〜１０、好ましくは２〜１０の二価の炭化水素基を示すが、ここで炭素数１〜１０の二価の炭化水素基とは、具体的にはメチレン基；エチレン基；フェニルエチレン基；１，２−プロピレン基；２−フェニル−１，２−プロピレン基；１，３−プロピレン基；各種ブチレン基；各種ペンチレン基；各種ヘキシレン基；各種ヘプチレン基；各種オクチレン基；各種ノニレン基；各種デシレン基の二価の脂肪族基、シクロヘキサン；メチルシクロヘキサン；エチルシクロヘキサン；ジメチルシクロヘキサン；プロピルシクロヘキサンなどの脂環式炭化水素に２個の結合部位を有する脂環式基、各種フェニレン基；各種メチルフェニレン基；各種エチルフェニレン基；各種ジメチルフェニレン基；各種ナフチレン基などの二価の芳香族炭化水素基、トルエン；キシレン；エチルベンゼンなどのアルキル芳香族炭化水素のアルキル基部分と芳香族部分にそれぞれ一価の結合部位を有するアルキル芳香族基、キシレン；ジエチルベンゼンなどのポリアルキル芳香族炭化水素のアルキル基部分に結合部位を有するアルキル芳香族基などを挙げることができる。これらの中で炭化数２〜４の脂肪族基が特に好ましい。
【００４６】
なお、前記一般式（２）におけるｐはＲ⁸ Ｏの繰り返し数を示し、その平均値が０〜１０、好ましくは０〜５の範囲の数である。Ｒ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。
さらに、前記一般式（２）におけるＲ⁹ は炭素数１〜２０、好ましくは１〜１ ０の炭化水素基を示すが、この炭化水素基とは、具体的にはメチル基，エチル基，ｎ−プロピル基，イソプロピル基，各種ブチル基，各種ペンチル基，各種ヘキシル基，各種ヘプチル基，各種オクチル基，各種ノニル基，各種デシル基のアルキル基、シクロペンチル基，シクロヘキシル基，各種メチルシクロヘキシル基，各種エチルシクロヘキシル基，各種プロピルシクロヘキシル基，各種ジメチルシクロヘキシル基などのシクロアルキル基、フェニル基，各種メチルフェニル基，各種エチルフェニル基，各種ジメチルフェニル基，各種プロピルフェニル基，各種トリメチルフェニル基，各種ブチルフェニル基，各種ナフチル基などのアリール基、ベンジル基，各種フェニルエチル基，各種メチルベンジル基，各種フェニルプロピル基，各種フェニルブチル基のアリールアルキル基などを挙げることができる。
【００４７】
このビニルエーテルモノマーとしては、例えばビニルメチルエーテル；ビニルエチルエーテル；ビニル−ｎ−プロピルエーテル；ビニル−イソプロピルエーテル；ビニル−ｎ−ブチルエーテル；ビニル−イソブチルエーテル；ビニル−ｓｅｃ−ブチルエーテル；ビニル−ｔｅｒｔ−ブチルエーテル；ビニル−ｎ−ペンチルエーテル；ビニル−ｎ−ヘキシルエーテル；ビニル−２−メトキシエチルエーテル；ビニル−２−エトキシエチルエーテル；ビニル−２−メトキシ−１−メチルエチルエーテル；ビニル−２−メトキシ−２−メチルエーテル；ビニル−３，６−ジオキサヘプチルエーテル；ビニル−３，６，９−トリオキサデシルエーテル；ビニル−１，４−ジメチル−３，６−ジオキサヘプチルエーテル；ビニル−１，４，７−トリメチル−３，６，９−トリオキサデシルエーテル；ビニル−２，６−ジオキサ−４−ヘプチルエーテル；ビニル−２，６，９−トリオキサ−４−デシルエーテル；１−メトキシプロペン；１−エトキシプロペン；１−ｎ−プロポキシプロペン；１−イソプロポキシプロペン；１−ｎ−ブトキシプロペン；１−イソブトキシプロペン；１−ｓｅｃ−ブトキシプロペン；１−ｔｅｒｔ−ブトキシプロペン；２−メトキシプロペン；２−エトキシプロペン；２−ｎ−プロポキシプロペン；２−イソプロポキシプロペン；２−ｎ−ブトキシプロペン；２−イソブトキシプロペン；２−ｓｅｃ−ブトキシプロペン；２−ｔｅｒｔ−ブトキシプロペン；１−メトキシ−１−ブテン；１−エトキシ−１−ブテン；１−ｎ−プロポキシ−１−ブテン；１−イソプロポキシ−１−ブテン；１−ｎ−ブトキシ−１−ブテン；１−イソブトキシ−１−ブテン；１−ｓｅｃ−ブトキシ−１−ブテン；１−ｔｅｒｔ−ブトキシ−１−ブテン；２−メトキシ−１−ブテン；２−エトキシ−１−ブテン；２−ｎ−プロポキシ−１−ブテン；２−イソプロポキシ−１−ブテン；２−ｎ−ブトキシ−１−ブテン；２−イソブトキシ−１−ブテン；２−ｓｅｃ−ブトキシ−１−ブテン；２−ｔｅｒｔ−ブトキシ−１−ブテン；２−メトキシ−２−ブテン；２−エトキシ−２−ブテン；２−ｎ−プロポキシ−２−ブテン；２−イソプロポキシ−２−ブテン；２−ｎ−ブトキシ−２−ブテン；２−イソブトキシ−２−ブテン；２−ｓｅｃ−ブトキシ−２−ブテン；２−ｔｅｒｔ−ブトキシ−２−ブテンなどを挙げることができる。
【００４８】
これらのビニルエーテルモノマーは、公知の方法により製造することができる。
上記のモノマ−のうち、エチルビニルエ−テルとイソプロピルビニルエ−テル 又はイソブチルビニルエ−テルの混合物であり、その割合が１００〜５０：０〜５０（モル％）、さらには１００〜７０：０〜３０（モル％）のものが特に好ましい。
【００４９】
なお、モノマ−としてビニルエ−テル化合物と炭化水素系モノマ−を併用することも可能である。従って、上記一般式（２）のビニルエ−テル化合物と上記一般式（１）の炭化水素系ビニル化合物とを併用し、両者の共重合体つまり、一般式（２）のモノマ−１種又は２種以上と一般式（１）のモノマ−１種又は２種以上を原料モノマ−として重合することもできる。
【００５０】
この場合、上記一般式（２）のモノマ−と一般式（１）のモノマ−との混合割合は１００〜５０：０〜５０（モル％）、さらには、９５〜７０：５〜３０（モル％）である場合が好ましい。
次に、上記のモノマ−を重合する場合に使用する触媒（重合触媒）は、ブレンステッド酸類、ルイス酸類、有機金属化合物類等があり、ブレンステッド酸類としては、フッ化水素酸、塩化水素酸、臭化水素酸、ヨウ化水素酸、硝酸、硫酸、トリクロロ酢酸、トリフルオロ酢酸などが挙げられ、ルイス酸類としては、三フッ化ホウ素及びその錯体類、三塩化アルミニウム、三臭化アルミニウム、四塩化スズ、二塩化亜鉛、塩化第二鉄などが挙げられる。また、有機金属化合物類としては、ジエチル塩化アルミニウム、エチル塩化アルミニウム、ジエチル亜鉛などが挙げられる。
【００５１】
これらのうち、三フッ化ホウ素及びその錯体類、例えば、三フッ化ホウ素の水錯体、アルコ−ル（メチルアルコ−ル、エチルアルコ−ル、ｎ−プロピルアルコ−ル、イソプロピルアルコ−ル、ｎ−ブチルアルコ−ル、イソブチルアルコ−ル等の）錯体、ジエチルエ−テル錯体が特に好ましい。なお、上記の触媒とともに重合開始剤を併用すると反応が促進する場合がある。
【００５２】
次に、このモノマ−の重合反応に用いる連鎖移動剤としては、水、アルコ−ル類、フエノ−ル類等がある。
ここで、アルコ−ル類としては、例えばメタノ−ル、エタノ−ル、プロパノ−ル、イソプロパノ−ル、ブタノ−ル、イソブタノ−ル、ｓｅｃ−ブタノ−ル、ｔｅｒｔ−ブタノ−ル、各種ペンタノ−ル、各種ヘキサノ−ル、各種ヘプタノ−ル、各種オクタノ−ルなどの炭素数１〜２０の飽和脂肪族アルコ−ル、アリルアルコ−ルなどの炭素数３〜１０の不飽和脂肪族アルコ−ルなどが挙げられる。
【００５３】
これらのうちメタノ−ル、エタノ−ル、プロパノ−ル、イソプロパノ−ル、ブタノ−ル、イソブタノ−ル、ｓｅｃ−ブタノ−ル、ｔｅｒｔ− ブタノ−ル、各種ペンタノ−ル、各種ヘキサノ−ル等低級炭化水素のアルコ−ルが好ましく、なかでもエタノ−ルが好ましい。
なお、重合反応には溶媒を用いて行ってもよい。その場合使用する溶剤は、ヘキサン、ヘプタン、オクタン、ノナン等の直鎖又は分岐の飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素、テトラヒドロフラン等の極性化合物で不活性な溶媒が挙げられる。溶媒の使用量は製造する重合体の分子量によって異なり、一般に分子量が大きい程反応系の粘度が上昇するため、通常目的の重合体の分子量が大きい場合は溶媒を多量に投入する。
【００５４】
以上の原材料等を使用して、ビニルエ−テル化合物の重合体を次のように製造する。なお、以下の重合反応はカチオン重合反応の例である。
（１）まず、反応槽に触媒を投入する。
触媒としてのいわゆる重合開始剤の投入量としては、重合体の分子量が３００〜５００００のものを得る場合は通常全モノマー量の１／１００００〜１／２（モル）である。
【００５５】
一方、いわゆる重合触媒の投入量は、重合開始剤量の１／６００〜１／３０（モル）の割合で配合する。
重合触媒の量が重合開始剤の１／６００未満では、重合反応の速度が遅くなることがあり、１／３０以上では、副反応が起こる場合があり、また重合物が着色することがある。
なお、溶媒を使用する場合は、触媒投入前に配合するのが好ましい。
（２）次いで、反応温度と反応圧力を設定する。
【００５６】
反応温度は通常０〜１００℃，好ましくは０〜５０℃の範囲の温度で行う。
また反応圧力は通常３ｋｇ／ｃｍ² 以下で行う。
（３）続いて、連鎖移動剤とモノマ−を逐次供給する。
連鎖移動剤の供給量は、通常モノマ−に対し０．０２〜１．０重量％であり、これを連続的又は断続的に逐次供給する。
（４）以上の条件を維持しながら反応終了まで重合を続ける。
【００５７】
反応は発熱を伴うので、通常除熱しながら実施する。反応は通常１〜１０時間程度実施する。なお必要に応じて反応系を不活性ガス等でパ−ジして行う。
以上の方法で、目的の分子量分布が狭い重合体を得ることができる。
なお、上述の重合方法で得られた重合体を、より安定な化合物にするために、さらに、水素化することが好ましい。
【００５８】
水素化の方法は特に制限はなく、いかなる方法でもよい。例えば、ニッケル−シリカアルミナ、ニッケル−ジルコニア、ニッケル−珪藻土などの担持型ニッケル触媒の存在下、水素圧力３〜８０ｋｇ／ｃｍ² ，好ましくは３〜５０ｋｇ／ｃｍ² ，特に好ましくは１０〜５０ｋｇ／ｃｍ² ，反応温度９０〜２００℃、好ましくは１００〜１７０℃で水素化する方法によって効率よく行うことができる。
【００５９】
また、この水素化反応は、懸濁床回分式、固定床連続式のいずれの方法でもよい。
〔重合体〕
本発明の重合体は、ビニルエ−テル化合物の重合体又は共重合体であって、重合体の重量平均分子量が３００〜５００００であり、かつ、分子量分布のピ−ク強度の最大値に該当する分子量の３倍以上の分子量を有する重合体の含有量が全重合体の１重量％以下である重合体である。
【００６０】
すなわち、本発明の重合体は、分子量分布，すなわち分子量分布曲線のピ−ク強度の最大値に該当する分子量の３倍以上の分子量を有する重合物の含有量が前記重合体の１重量％以下である。
ここでいう、分子量分布曲線とは、通常ゲルパ−ミィエ−ションクロマトグラフィ−（以下「ＧＰＣ」という）によって得られる曲線（クロマトグラム）をいう。図を用いて説明すると、図１は、分子量分布曲線、つまり、ＧＰＣクロマトグラムの概念図であり、縦軸がピ−ク強度、横軸が分子量を表している。この図で、（１）がピ−ク強度が最大値の点、すなわち主成分の重合体に該当する分子量の点である。また、（２）が主成分の分子量の３倍の分子量に該当する点である。従って、本発明の重合体は、図１の分子量分布曲線で、（２）の点より右側の面積が分子量分布曲線の全面積の１％以下であることになる。なお、このＧＰＣによる分子量分布曲線の面積比は、通常重量％に相当する。
【００６１】
以上のことは、本発明の重合体の分子量分布は狭く、シャ−プであることを示している。
さらにまた、本発明の重合体は、〔重量平均分子量〕／〔数平均分子量〕で表した分子量分布が２．５以下、さらには２．０、特に１．５以下であることが好ましい。ここでいう分子量分布も、ＧＰＣによって得られる重量平均分子量と数平均分子量の比から求められる。
【００６２】
この分子量分布の理論的下限は，１．００であるが、通常小さい場合でも１．０５程度になるから、分子量分布の範囲は１．０５〜２．５，さらには１．０５〜１．５が好ましい範囲である。
ついで、本発明の重合体は、ビニルエ−テル化合物の重体又は共重合体であって、重合体の重量平均分子量が３００〜５００００、好ましくは３００〜１００００、特に好ましくは３００〜５０００のものである。
【００６３】
ここでいうモノマ−としてのビニルエ−テル化合物は、ビニルエ−テル化合物が主成分であればよく、一定量以下のビニルエ−テル化合物以外のモノマ−、例えば炭化水素系ビニル化合物を含んでいてもよい。
従って、本発明の重合体は、ビニルエ−テル化合物の重合体又は共重合体の他に、少なくとも１種のビニルエ−テル化合体と少なくとも１種の炭化水素系ビニル化合物との共重合体をも含む概念である。
【００６４】
ビニルエ−テル化合体と炭化水素系ビニル化合物の割合は、１００〜５０：０〜５０（モル％）、さらには、１００〜７０：０〜３０（モル％）であるものが好ましい。
なお、上記の共重合体には、ランダム重合体及びブロック重合体が含まれる。
以上述べたビニルエ−テル化合物の重合体又は共重合体は、通常末端アセタ−ル基等を有するが、これを除去した重合体であれば、さらに安定な重合体となる。末端アセタ−ル基等を除去した重合体は、上述の重合体を水素化することによって得ることができる。
【００６５】
上記の重合物の製造方法については、特に制限はないが、前述の〔重合体の製造方法〕で述べた方法によって、重合し、必要に応じて水素化することにより製造すれば、効率的に製造できる。
上記のビニルエ−テル化合物の重合体又は共重合体の代表例としては、一般式（３）で表される構成単位、又は一般式（３）と一般式（４）で表される構成単位からなり、その重合体の末端が一般式（５）又は（６）及び一般式（７）又は（８）である重合体が挙げられる。
【００６６】
【化２３】

【００６７】
（式中、Ｒ⁵ 〜Ｒ⁷ はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ⁸ は炭素数１〜１０の二価の炭化水素基、Ｒ⁹ は炭素数１〜２０の炭化水素基、ｐはその平均値が０〜１０の数を示し、Ｒ⁵ 〜Ｒ⁹ は構成単位毎に同一でもそれぞれ異なっていてもよく、またＲ⁸ Ｏが複数ある場合には、複数のＲ⁸ Ｏは同一でも異なっていてもよい。）
【００６８】
【化２４】

【００６９】
（式中、Ｒ¹ 〜Ｒ⁴ は水素原子又は炭素数１〜１２の炭化水素基を示す。）
【００７０】
【化２５】

【００７１】
（式中、Ｒ⁵ 〜Ｒ⁹ 及びｐは前記一般式（２）と同じ）
【００７２】
【化２６】

【００７３】
（式中、Ｒ¹ 〜Ｒ⁴ は前記一般式（４）と同じ）
【００７４】
【化２７】

【００７５】
（式中、Ｒ⁵ 〜Ｒ⁹ 及びｐは前記一般式（３）と同じ）
【００７６】
【化２８】

【００７７】
（式中、Ｒ¹ 〜Ｒ⁴ は前記一般式（４）と同じ）
この中で、構成単位が一般式（３）で表され、重合体の末端が一般式（５）と一般式（７）で表される重合体で、一般式（３），（５）及び（７）のｐが０で、Ｒ⁹ がエチル基である構成単位とｐが０でＲ⁹ がイソプロピル基若しくはイソブチル基である構成単位からなり、その割合が１００〜５０：０〜５０（モル比）、さらには１００〜７０：０〜３０の重合体が特に好適に用いられる。
〔重合体の冷凍機用潤滑油への用途〕
上記重合体は種々の用途に利用できる。例えば、溶剤、潤滑油、接着剤、樹脂などに有用であり、主成分に該当する分子量の３倍以上の分子量を有する重合体が１重量％以上の重合体と比較して、流動性、安定性及びそれぞれ固有の性能が向上する効果がある。
【００７８】
特に、上記重合体は冷凍機用潤滑油として有効であり、冷媒であるハイドロフルオロカ−ボン（ＨＦＣ）との溶解性が著しく向上する。また、冷媒がアンモニア、ハイドロカーボン、二酸化炭素等の場合も同様である。
従って、本発明の重合体が適用される冷凍機に用いられる冷媒としては、ハイドロフルオロカーボン，フルオロカーボン，ハイドロカーボン，エーテル，二酸化炭素又はアンモニア冷媒が用いられる。これらの中でハイドロフルオロカーボン冷媒としては、例えば１，１，１，２−テトラフルオロエタン（Ｒ１３４ａ），ジフルオロメタン（Ｒ３２），ペンタフルオロエタン（Ｒ１２５）及び１，１，１−トリフルオロエタン（Ｒ１４３ａ）が挙げられ、これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、混合冷媒の例としては、Ｒ３２とＲ１２５とＲ１３４ａとの重量比２３：２５：５２の混合物（以下、Ｒ４０７Ｃと称する。），重量比２５：１５：６０の混合物，Ｒ３２とＲ１２５との重量比５０：５０の混合物（以下、Ｒ４１０Ａと称する。），Ｒ３２とＲ１２５との重量比４５：５５の混合物（以下、Ｒ４１０Ｂと称する。），Ｒ１２５とＲ１４３ａとＲ１３４ａとの重量比４４：５２：４の混合物（以下、Ｒ４０４Ａと称する。），Ｒ１２５とＲ１４３ａとの重量比５０：５０の混合物（以下、Ｒ５０７と称する。）などを挙げることができる。
【００７９】
【実施例】
本発明について、更に、実施例を用いて詳細に説明する。
なお、実施例で用いた試験方法は、以下のとおりである。
〔分子量分布の測定方法〕
高速液体クロマトグラフィ−（高速ＧＰＣ）による溶出曲線から重量平均分子量と数平均分子量を求め、重量平均分子量／数平均分子量を分子量分布として算出した。測定条件は下記の通りである。
【００８０】
カラム：ＴＳＫ Ｇ３０００Ｈ８＋Ｇ２０００Ｈ８＋Ｇ１０００Ｈ８
移動相：特級ＴＨＦ
流速：１．４ｍｌ／ｍｉｎ
試料溶解方法：移動相溶媒に溶解（サンプル濃度 ２ｍｇ／ｍｌ）
試料注入量：４００μｌ
検出器：ＲＩ（示差屈折）検出器、セル温度４０℃
検量線作成用標準資料：ポリエチレングリコ−ル及びポリスチレン
〔二層分離温度の測定〕
試料０．４５ｇを耐圧ガラスアンプルに秤量し、これを真空配管及びハイドロフルオロカ−ボン混合冷媒（Ｒ４１０Ａ）配管に接続した。アンプルを室温で真空脱気後、Ｒ４１０Ａ冷媒２．５５ｇを液体状で採取した。次いで、アンプルを封じ、恒温槽中で室温から−５０℃まで徐徐に冷却して層分離が始まる温度を測定した。
〔比較例１〕
エチルアルコ−ル２２４８ｇ、イソブチルアルコ−ル４０２ｇ，三フッ化ホウ素ジエチルエ−テル錯体２１．４ｇ及びイソノナン１５．２リットルを１００ リットルの反応容器に仕込んだ後、反応温度を４５℃に保持した。この反応容器へエチルビニルエ−テル４１．５ｋｇとイソブチルビニルエ−テル６．４ｋｇの混合物を５時間連続的に供給した。得られた重合物のＧＰＣによる分子量分布曲線は、分子量９２０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝２７６０）以上の重合体は１．５８％であった。
〔実施例１〕
比較例１の、エチルビニルエ−テルとイソブチルビニルエ−テルの混合物の代わりに、ここ混合部に更に、エタノ−ル１０００ｐｐｍ（４８ｇ）を加えた混合物を連続的に供給したこと以外は、比較例１と同様の方法で重合した。
【００８１】
得られた重合物の高速ＧＰＣによる分子量分布曲線は、分子量９１０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝２７３０）以上の重合体は０．８１％であった。また、分子量分布は１．１８であった。
〔比較例２〕
エチルアルコ−ル２６ｋｇ、イソブチルアルコ−ル５ｋｇ，三フッ化ホウ素ジエチルエ−テル錯体２５０ｇ及びトルエン３７９ｋｇを３ｍ³ の反応容器に仕込んだ後、反応温度を２５℃に保持した。この反応容器へエチルビニルエ−テル５２０ｋｇとイソブチルビニルエ−テル８０ｋｇの混合物を８時間連続的に供給した。得られた重合物の高速ＧＰＣによる分子量分布曲線は、分子量７８０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝２３４０）以上の重合体は１．３３％であった。
〔実施例２〕
比較例２の製造条件で、エチルビニルエ−テルとイソブチルビニルエ−テルの混合物を連続的に供給している期間、反応装置の気相部を攪拌翼で攪拌しながらエタノ−ルを６０℃に加熱した窒素ガスとともに２００ｇ／時間の速度で気相部へ供給して重合体を製造した。また、分子量分布は１．１９であった。
【００８２】
得られた重合物の高速ＧＰＣによる分子量分布曲線は、分子量７５０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝２２５０）以上の重合体は０．６８％であった。
〔比較例３〕
含水トルエン（水分３５０ｐｐｍ）６０ｍｌ、三フッ化ホウ素ジエチルエ−テル錯体１．０ｇを２００ｍｌの４つ口フラスコに入れ、反応温度２５℃に保持した。そこへスチレン４１．７ｇを約４５分かけて連続的に供給して重合した。得られた重合物の高速ＧＰＣによる分子量分布曲線は、分子量３７３０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝１１１９０）以上の重合体は４．１０％であった。
〔実施例３〕
比較例３のスチレンに代えて、スチレンにエタノ−ル３００ｐｐｍ（０．０４ｇ）加えた混合物を供給して重合体を製造した。得られた重合物の高速ＧＰＣによる分子量分布曲線は、分子量３３３０をピ−ク強度の最大値とするものであり、また、分子量がピ−ク強度の最大値の分子量×３（＝９９９０）以上の重合体は２．９３％であった。また、分子量分布は２．２０であった。
〔実施例４、５及び比較例４，５〕
実施例１、２及び比較例１，２で得た重合体を水素化し、その水素化物の冷媒Ｒ４１０Ａに対する二層分離温度を測定した。測定結果を表１に示した。
【００８３】
なお、水素化方法は次のようにして行った。
触媒の調整
ＳＵＳ３１６Ｌ製２リットルのオ−トクレ−ブにニッケル珪藻土触媒（日揮化学社製、商品Ｎ１１３）１２ｇ及びイソオクタン３００ｇを仕込んだ。オ−トクレ−ブ内を窒素置換し、次いで水素置換したのち、水素圧を３０ｋｇ／ｃｍ² Ｇとし昇温し１４０℃で３０分間保持後、室温まで冷却した。オ−トクレ−ブ内を窒素置換したのち、オ−トクレ−ブにアセトアルデヒドジエチルアセタ−ルを２０ｇ加え、再び窒素置換し、次いで水素置換後、水素圧を３０ｋｇ／ｃｍ² Ｇとして昇温した。１３０℃で３０分間保持後、室温まで冷却した。昇温によりオ−トクレ−ブ内の圧力が上昇する一方、アセトアルデヒドジエチルアセタ−ルが反応することにより、水素圧力の減少が認められた。圧力が減少し、３０ｋｇ／ｃｍ² Ｇ以下となった場合は水素を足し３０ｋｇ／ｃｍ² Ｇとした。室温まで冷却脱圧し、次いで、オ−トクレ−ブ内を窒素置換した後脱圧した。
【００８４】
ビニルエ−テル重合体の水素化
上記の触媒の調整で得た触媒入りオ−トクレ−ブを開放し、液層をデカンテ−ションで除去したのち実施例１で得られた重合物４００ｇを入れた。オ−トクレ−ブ内を窒素置換し、次いで水素置換したのち、水素圧を３０ｋｇ／ｃｍ² Ｇとし昇温した。１４０℃で２時間保持後、室温まで冷却した。昇温によりオ−トクレ−ブ内の圧力が上昇する一方、反応の進行により水素圧力の減少が認められた。圧力が減少した場合、適時水素を加えオ−トクレ−ブ内を３０ｋｇ／ｃｍ² Ｇとした。オ−トクレ−ブ内を窒素置換した後脱圧し、反応液を回収してイソオクタン１００ｇを加え、ろ過して触媒を除いた。ろ液をロ−タリ−エバポレ−タで減圧処理して溶媒及び軽質分を除去して実施例４の試料を得た。
【００８５】
同様の方法で、実施例２，比較例１及び比較例２の重合体から実施例５、比較例４及び比較例５の試料を得た。
【００８６】
【表１】

【００８７】
【発明の効果】
（１）触媒の存在下でモノマ−を逐次供給しながら重合する重合体の製造方法において、連鎖移動剤を逐次供給して重合体を製造すると、その重合体は分子量分布が狭く、シャ−プになる。
（２）重合体がポリビニルエ−テル化合物の重合体又は共重合体であって、重合体の重量平均分子量が３００〜５００００であり、かつ、分子量分布曲線のピ−ク強度の最大値に該当する分子量の３倍以上の分子量を有する重合体の含有量が全重合体の１重量％以下である重合体を主成分とする冷凍機用潤滑油は、冷媒との溶解性が高い。
【図面の簡単な説明】
【図１】 本発明の重合方法によって得られる重合体のＧＰＣによる分子量
分布曲線の概念図である。
【符号の説明】
（１） 分子量分布曲線のピ−ク強度が最大値に該当する分子量の点
（２） 分子量分布曲線のピ−ク強度が最大値に該当する分子量の３倍の
分子量の点[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a novel polymer, mainly a polymer produced by the production method and uses of the polymer. More specifically, a method for producing a polymer in which a polymerization reaction is performed by adjusting a method for supplying a chain transfer agent, a polymer having a narrow molecular weight distribution produced by such a method, and use of the polymer as a lubricating oil About.
[0002]
[Prior art]
When a polymer such as an oligomer or a polymer is produced by polymerizing a monomer, it may be preferable that the polymer has a narrow molecular weight distribution. This is because if a polymer having a wide molecular weight distribution is put into practical use for various uses in the industry, it may be difficult to exhibit the required performance. For example, when a polymer having a wide molecular weight distribution is used for a lubricating oil for a refrigerator, the solubility between the lubricating oil and chlorofluorocarbon as a refrigerant is lowered.
[0003]
Therefore, the production of a sharp polymer having a narrow molecular weight for the target polymer is an extremely important technical issue, and there is a demand for technological development.
The method for producing such a polymer having a narrow molecular weight distribution includes selecting the type and amount of catalyst, controlling the amount of chain transfer agent, adjusting the method of using a polymerization terminator, or the reaction temperature and reaction time. A method such as controlling the above is conceivable.
[0004]
However, using any of these methods, it is difficult to control the molecular weight distribution narrowly on an industrial scale, and there are known examples such as polyalkylene glycol that can produce a polymer having a narrow molecular weight distribution regardless of the production method. It has only been done.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a sharp polymer having a narrow molecular weight distribution, mainly a polymer produced by such a method, and a use for a lubricating oil utilizing the properties of the polymer. And
[0006]
[Means for Solving the Problems]
In the present invention, the molecular weight distribution of the polymer obtained by polymerizing the monomer can be controlled by adjusting the supply method of the chain transfer agent used at the time of polymerization, and the polymer whose molecular weight distribution satisfies a specific condition is used for lubricating oil. It has been found out that it exhibits a specific effect in such a case, and has been completed based on such knowledge. Therefore, the gist of the present invention is as follows.
[0007]
[1] A method for producing a polymer in which a chain transfer agent is successively fed in a polymer producing method in which polymerization is carried out while successively feeding monomers in the presence of a catalyst.
[2] The method for producing a polymer according to the above [1], wherein the period from the start of supply of the chain transfer agent to the end of supply is not less than ½ of the monomer supply period.
[3] Production of a polymer as described in [1] or [2] above, wherein the chain transfer agent is previously mixed with a monomer, and the mixture of the chain transfer agent and the monomer is sequentially supplied to the reaction system. Method.
[0008]
[4] The method for producing a polymer according to any one of [1] or [2], wherein the chain transfer agent is vaporized and supplied to the gas phase portion of the reaction system.
[5] The polymer according to any one of [1] to [4], wherein the monomer is one or more compounds selected from hydrocarbon-based vinyl compounds represented by the general formula (1). Manufacturing method.
[0009]
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[0010]
(Wherein R¹~ R^FourRepresents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. )
[6] The polymer according to any one of [1] to [4] above, wherein the monomer is one or more compounds selected from vinyl ether compounds represented by the general formula (2). Production method.
[0011]
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[0012]
(Wherein R^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R⁸Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R⁹Is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R^Five~ R⁹May be the same or different for each structural unit, and R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different. )
[7] The monomer is selected from one or more compounds selected from the vinyl ether compounds represented by the general formula (2) and the hydrocarbon vinyl compounds represented by the general formula (1). The method for producing a polymer according to any one of the above [1] to [4], wherein the polymer is one kind or two or more kinds of compounds.
[0013]
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[0014]
(Wherein R^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R⁸Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R⁹Is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R^Five~ R⁹May be the same or different for each structural unit, and R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different. )
[0015]
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[0016]
(Wherein R¹~ R^FourRepresents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. )
[8] The method for producing a polymer according to any one of [1] to [7], wherein the polymerization reaction is a cationic polymerization reaction.
[9] The above [1] to [8], wherein the polymer has a weight average molecular weight of 300 to 50,000 and the polymer has a molecular weight distribution ([weight average molecular weight] / [number average molecular weight]) of 2.5 or less. The manufacturing method of the polymer in any one of.
[0017]
[10] The above [1] to [1], wherein the content of the polymer having a molecular weight not less than 3 times the molecular weight corresponding to the maximum peak strength in the molecular weight distribution curve of the polymer is 1% by weight or less of the total polymer. [9] The method for producing a polymer according to any one of [9].
[11] A method for producing a polymer which is polymerized by the method according to any one of [1] to [10] and then hydrogenated.
[0018]
[12] The polymer is a polymer or copolymer of a vinyl ether compound, the polymer has a weight average molecular weight of 300 to 50,000, and corresponds to the maximum peak strength of the molecular weight distribution curve. A polymer in which the content of a polymer having a molecular weight of 3 times or more of the molecular weight is 1% by weight or less of the total polymer.
[13] A polymer obtained by hydrogenating the polymer described in [12].
[0019]
[14] The structural unit of the polymer is represented by the general formula (3), or the structural unit of the polymer is represented by the general formulas (3) and (4), and the terminal thereof is represented by the general formula (5) or (6). And the polymer according to the above [13], which is represented by the general formula (7) or (8).
[0020]
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[0021]
(Wherein R^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R⁸Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R⁹Is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R^Five~ R⁹May be the same or different for each structural unit, and R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different. )
[0022]
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[0023]
(Wherein R¹~ R^FourRepresents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. )
[0024]
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[0025]
(Wherein R^Five~ R⁹And p are the same as those in the general formula (3))
[0026]
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[0027]
(Wherein R¹~ R^FourIs the same as in the general formula (4))
[0028]
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[0029]
(Wherein R^Five~ R⁹And p are the same as those in the general formula (3))
[0030]
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[0031]
(Wherein R¹~ R^FourIs the same as in the general formula (4))
[15] A compression refrigerator comprising as a main component a polymer produced by the production method described in [10] or [11] or the polymer described in any one of [12] to [14]. Lubricating oil.
[0032]
DETAILED DESCRIPTION OF THE INVENTION
[Production method of polymer]
The method for producing a polymer of the present invention is a method for producing a polymer, wherein a chain transfer agent is sequentially supplied in a polymerization method in which a monomer is successively supplied in the presence of a catalyst.
[0033]
If the chain transfer agent is not fed at a time but polymerized by successively feeding, there is an effect of controlling the molecular weight distribution of the polymer and producing a polymer having a narrow molecular weight distribution. This method can be applied to any polymerization mode such as bulk polymerization and solution polymerization regardless of radical polymerization or ionic polymerization.
The molecular weight of the polymer produced by this method is not particularly limited, but it is preferable and effective when producing a polymer having a weight average molecular weight of about 300 to 50,000, more preferably 300 to 10,000, and particularly 300 to 5,000.
[0034]
The term “chain transfer agent” as used herein refers to a compound having a wide chain transfer function. For example, ethylbenzene, isopropylbenzene, chloroform and the like are used for radical polymerization, and water, alcohols and the like are used for anion polymerization. In polymerization, compounds such as water, alcohols and amines can be exemplified.
“Sequential supply” of the chain transfer agent means that the chain transfer agent is supplied in a dispersed manner during the polymerization reaction period, not at the beginning of the reaction.
[0035]
Therefore, as long as it is distributed and supplied, it may be supplied intermittently or continuously. In this case, the higher the ratio of the period (time) for supplying the chain transfer agent to the monomer supply period (time), the more remarkable the effect of narrowing the molecular weight distribution, and the ratio is 1/2 or more. Further, it is preferable to supply 3/4 or more, particularly 1/1, that is, for the entire period.
[0036]
A particularly preferred embodiment is a method in which the chain transfer agent is supplied roughly in proportion to the amount of monomer supplied, and in that respect, a method in which the chain transfer agent is continuously supplied throughout the entire monomer supply period is preferred.
Specifically, a method of supplying the chain transfer agent separately to the reaction system separately from the monomer and a method of supplying the chain transfer agent as a mixture with the monomer by mixing the chain transfer agent with the monomer can be mentioned.
[0037]
Moreover, when supplying a chain transfer agent independently, this can be heated and vaporized, and can also be supplied to a reaction system in a gaseous state. In this case, if the vaporized chain transfer agent is supplied to the gas phase part of the reaction system, the chain transfer agent dissolves from the liquid interface, acts uniformly on the reaction part, and prevents overpolymerization in the gas phase part. A polymer having a narrow molecular weight distribution may be obtained. The vaporized chain transfer agent can be supplied together with an accompanying gas such as nitrogen gas.
[0038]
The polymerization method of the present invention based on the premise of sequentially supplying monomers is such that when a highly reactive monomer is polymerized, the polymerization reaction runs away by supplying the monomer at an early stage of the reaction. It also has the effect of preventing danger.
The “catalyst” as used in the present invention is a substance that accelerates the polymerization reaction, and means a so-called polymerization catalyst and a polymerization initiator in a narrow sense. Therefore, there are a case where only one of a so-called polymerization catalyst and a polymerization initiator is used as a catalyst, and a case where both are used in combination. The polymerization catalyst referred to here is a concept that includes not only ordinary tangible catalysts but also intangible ones such as light, heat, and radiation.
[0039]
In the method for producing a polymer of the present invention, a chain transfer agent is sequentially supplied in the presence of the above-mentioned catalyst, and a reaction temperature, a reaction pressure, and a reaction time are obtained by sequentially supplying a chain transfer agent. Just do it.
The monomer used in the present invention is not particularly limited, and any monomer can be used.
Speaking of vinyl compounds, there are hydrocarbon monomers, polar monomers, and cyclic monomers. In the case of hydrocarbon monomers (hydrocarbon vinyl compounds), those represented by general formula (1) are included. It is.
[0040]
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[0041]
(Wherein R¹~ R^FourRepresents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. )
The hydrocarbon group of the general formula (1) includes a linear or branched saturated or unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group.
Suitable hydrocarbon vinyl monomers represented by the general formula (1) include, for example, ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, various Examples thereof include alkyl-substituted styrene.
[0042]
Next, the production method of the present invention will be described more specifically by taking as an example the case of polymerizing a vinyl ether compound which is a polar monomer among vinyl compounds.
Examples of the vinyl ether monomer used in the present invention include those represented by the general formula (2).
[0043]
Embedded image

[0044]
(Wherein R^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R⁸Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R⁹Is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R^Five~ R⁹May be the same or different for each structural unit, and R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different. )
R in the general formula (2)^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. The hydrocarbon group specifically means a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl group alkyl groups, cyclopentyl. Groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, cycloalkyl groups such as various dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, aryl groups of various dimethylphenyl groups, benzyl groups, various types Mention may be made of phenylethyl groups and arylalkyl groups of various methylbenzyl groups. These R^Five~ R⁷Is particularly preferably a hydrogen atom.
[0045]
On the other hand, R in the general formula (2)⁸Represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms. Here, the divalent hydrocarbon group having 1 to 10 carbon atoms is specifically a methylene group; an ethylene group. Phenylethylene group, 1,2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups; Various nonylene groups; divalent aliphatic groups of various decylene groups, cyclohexane; methylcyclohexane; ethylcyclohexane; dimethylcyclohexane; alicyclic hydrocarbons having two bonding sites on alicyclic hydrocarbons such as propylcyclohexane, various phenylenes Groups; various methylphenylene groups; various ethylphenylene groups; various dimethylphenylene groups; various divalent aromatic groups such as naphthylene groups Xylide: Alkyl aromatic group having a monovalent bonding site in each of the alkyl group and aromatic part of an alkyl aromatic hydrocarbon such as ethylbenzene, xylene; Polyalkyl aromatic hydrocarbon such as diethylbenzene An alkyl aromatic group having a binding site in the alkyl group portion can be exemplified. Among these, an aliphatic group having 2 to 4 carbon atoms is particularly preferable.
[0046]
In the general formula (2), p is R⁸The repeating number of O is shown, and the average value is 0 to 10, preferably 0 to 5. R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different.
Furthermore, R in the general formula (2)⁹Represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, Various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups in various decyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethyls Cycloalkyl groups such as cyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, aryl groups such as benzyl Group, various phenylethyl groups, various methylbennes , And the like group, various phenylpropyl groups, arylalkyl groups various phenylbutyl groups.
[0047]
Examples of the vinyl ether monomer include vinyl methyl ether; vinyl ethyl ether; vinyl-n-propyl ether; vinyl-isopropyl ether; vinyl-n-butyl ether; vinyl-isobutyl ether; vinyl-sec-butyl ether; Vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-methoxyethyl ether; vinyl-2-ethoxyethyl ether; vinyl-2-methoxy-1-methylethyl ether; Vinyl-3,6-dioxaheptyl ether; vinyl-3,6,9-trioxadecyl ether; vinyl-1,4-dimethyl-3,6-dioxaheptyl ether; vinyl-1,4 7-trimethyl -3,6,9-trioxadecyl ether; vinyl-2,6-dioxa-4-heptyl ether; vinyl-2,6,9-trioxa-4-decyl ether; 1-methoxypropene; 1-ethoxypropene; 1-n-propoxypropene; 1-isopropoxypropene; 1-n-butoxypropene; 1-isobutoxypropene; 1-sec-butoxypropene; 1-tert-butoxypropene; 2-methoxypropene; 2-ethoxypropene; 2-n-propoxypropene; 2-isopropoxypropene; 2-n-butoxypropene; 2-isobutoxypropene; 2-sec-butoxypropene; 2-tert-butoxypropene; 1-methoxy-1-butene; Ethoxy-1-butene; 1-n-propoxy-1-butene; 1-isopro 1-n-butoxy-1-butene; 1-isobutoxy-1-butene; 1-sec-butoxy-1-butene; 1-tert-butoxy-1-butene; 2-methoxy-1- 2-ethoxy-1-butene; 2-n-propoxy-1-butene; 2-isopropoxy-1-butene; 2-n-butoxy-1-butene; 2-isobutoxy-1-butene; 2-sec 2-butoxy-1-butene; 2-tert-butoxy-1-butene; 2-methoxy-2-butene; 2-ethoxy-2-butene; 2-n-propoxy-2-butene; 2-isopropoxy-2- Examples include butene; 2-n-butoxy-2-butene; 2-isobutoxy-2-butene; 2-sec-butoxy-2-butene; 2-tert-butoxy-2-butene.
[0048]
These vinyl ether monomers can be produced by a known method.
Of the above monomers, a mixture of ethyl vinyl ether and isopropyl vinyl ether or isobutyl vinyl ether, the ratio of which is 100 to 50: 0 to 50 (mol%), and further 100 to 70: 0. 30 (mol%) is particularly preferred.
[0049]
It is also possible to use a vinyl ether compound and a hydrocarbon monomer together as the monomer. Therefore, the vinyl ether compound of the above general formula (2) and the hydrocarbon vinyl compound of the above general formula (1) are used in combination, that is, a copolymer of both, that is, a monomer of the general formula (2) -1 type or 2 It is also possible to polymerize one or more species and one or more monomers of the general formula (1) as raw material monomers.
[0050]
In this case, the mixing ratio of the monomer of the general formula (2) and the monomer of the general formula (1) is 100 to 50: 0 to 50 (mol%), and further 95 to 70: 5 to 30 (mol). %) Is preferred.
Next, catalysts (polymerization catalysts) used for polymerizing the above monomers include Bronsted acids, Lewis acids, organometallic compounds, etc., and Bronsted acids include hydrofluoric acid and hydrochloric acid. , Hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, etc., and Lewis acids include boron trifluoride and its complexes, aluminum trichloride, aluminum tribromide, tetra Examples include tin chloride, zinc dichloride, and ferric chloride. Examples of the organometallic compounds include diethyl aluminum chloride, ethyl aluminum chloride, diethyl zinc and the like.
[0051]
Among these, boron trifluoride and its complexes, for example, boron trifluoride water complex, alcohol (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n- Particularly preferred are complexes (such as butyl alcohol and isobutyl alcohol) and diethyl ether complexes. In addition, when a polymerization initiator is used in combination with the above catalyst, the reaction may be accelerated.
[0052]
Next, examples of the chain transfer agent used for the polymerization reaction of the monomer include water, alcohols and phenols.
Here, examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, and various pentaanols. , Various hexaanols, various heptanols, various octanols, etc., saturated aliphatic alcohols having 1 to 20 carbon atoms, unsaturated aliphatic alcohols having 3 to 10 carbon atoms such as allyl alcohol, etc. Is mentioned.
[0053]
Among them, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentaanols, various hexaanols, etc. Hydrocarbon alcohols are preferred, and ethanol is particularly preferred.
The polymerization reaction may be performed using a solvent. Examples of the solvent used in this case include linear or branched saturated hydrocarbons such as hexane, heptane, octane, and nonane, aromatic hydrocarbons such as benzene, toluene, and xylene, and polar solvents such as tetrahydrofuran. . The amount of solvent used varies depending on the molecular weight of the polymer to be produced. Generally, the larger the molecular weight, the higher the viscosity of the reaction system. Therefore, when the molecular weight of the target polymer is large, a large amount of solvent is usually added.
[0054]
Using the above raw materials and the like, a polymer of a vinyl ether compound is produced as follows. The following polymerization reaction is an example of a cationic polymerization reaction.
(1) First, a catalyst is put into the reaction vessel.
The input amount of a so-called polymerization initiator as a catalyst is usually 1/10000 to 1/2 (mol) of the total monomer amount when a polymer having a molecular weight of 300 to 50000 is obtained.
[0055]
On the other hand, the so-called polymerization catalyst is added in an amount of 1/600 to 1/30 (mol) of the polymerization initiator amount.
If the amount of the polymerization catalyst is less than 1/600 of the polymerization initiator, the rate of the polymerization reaction may be slow, and if it is 1/30 or more, side reactions may occur and the polymer may be colored.
In addition, when using a solvent, it is preferable to mix | blend before catalyst addition.
(2) Next, the reaction temperature and the reaction pressure are set.
[0056]
The reaction temperature is generally 0-100 ° C, preferably 0-50 ° C.
The reaction pressure is usually 3 kg / cm.²Do the following:
(3) Subsequently, a chain transfer agent and a monomer are sequentially supplied.
The supply amount of the chain transfer agent is usually 0.02 to 1.0% by weight based on the monomer, and this is continuously or intermittently supplied.
(4) The polymerization is continued until the end of the reaction while maintaining the above conditions.
[0057]
Since the reaction is exothermic, it is usually carried out with heat removal. The reaction is usually carried out for about 1 to 10 hours. If necessary, the reaction system is purged with an inert gas or the like.
By the above method, a target polymer having a narrow molecular weight distribution can be obtained.
In addition, in order to make the polymer obtained by the above-mentioned polymerization method into a more stable compound, it is preferable to further hydrogenate.
[0058]
The method for hydrogenation is not particularly limited, and any method may be used. For example, in the presence of a supported nickel catalyst such as nickel-silica alumina, nickel-zirconia, nickel-diatomaceous earth, a hydrogen pressure of 3-80 kg / cm², Preferably 3-50kg / cm², Particularly preferably 10-50 kg / cm², It can be carried out efficiently by a method of hydrogenation at a reaction temperature of 90 to 200 ° C., preferably 100 to 170 ° C.
[0059]
In addition, this hydrogenation reaction may be either a suspension bed batch method or a fixed bed continuous method.
(Polymer)
The polymer of the present invention is a polymer or copolymer of a vinyl ether compound, the polymer has a weight average molecular weight of 300 to 50,000, and corresponds to the maximum peak strength of the molecular weight distribution. It is a polymer in which the content of a polymer having a molecular weight 3 times or more of the molecular weight is 1% by weight or less of the total polymer.
[0060]
That is, the polymer of the present invention has a molecular weight distribution, that is, a content of a polymer having a molecular weight of 3 times or more the molecular weight corresponding to the maximum peak strength of the molecular weight distribution curve is 1% by weight or less of the polymer. It is.
The molecular weight distribution curve here refers to a curve (chromatogram) usually obtained by gel permeation chromatography (hereinafter referred to as “GPC”). Referring to the drawings, FIG. 1 is a conceptual diagram of a molecular weight distribution curve, that is, a GPC chromatogram, where the vertical axis represents peak intensity and the horizontal axis represents molecular weight. In this figure, (1) is the point where the peak strength is the maximum value, that is, the molecular weight corresponding to the main component polymer. Further, (2) corresponds to a molecular weight that is three times the molecular weight of the main component. Accordingly, in the polymer of the present invention, the area on the right side of the molecular weight distribution curve in FIG. 1 from the point (2) is 1% or less of the total area of the molecular weight distribution curve. The area ratio of the molecular weight distribution curve by GPC usually corresponds to wt%.
[0061]
The above shows that the molecular weight distribution of the polymer of the present invention is narrow and sharp.
Furthermore, the polymer of the present invention preferably has a molecular weight distribution represented by [weight average molecular weight] / [number average molecular weight] of 2.5 or less, more preferably 2.0, and particularly preferably 1.5 or less. The molecular weight distribution here is also determined from the ratio of the weight average molecular weight and the number average molecular weight obtained by GPC.
[0062]
The theoretical lower limit of this molecular weight distribution is 1.00, but it is usually about 1.05 even if it is small, so the range of the molecular weight distribution is 1.05 to 2.5, more preferably 1.05 to 1.5. Is a preferred range.
Next, the polymer of the present invention is a polymer or copolymer of a vinyl ether compound, and the polymer has a weight average molecular weight of 300 to 50,000, preferably 300 to 10,000, particularly preferably 300 to 5,000. .
[0063]
The vinyl ether compound as a monomer here may be a vinyl ether compound as a main component, and may contain a monomer other than a certain amount or less of a vinyl ether compound, for example, a hydrocarbon vinyl compound. .
Therefore, the polymer of the present invention includes a copolymer of at least one vinyl ether compound and at least one hydrocarbon vinyl compound in addition to the polymer or copolymer of the vinyl ether compound. It is a concept that includes.
[0064]
The ratio of the vinyl ether compound and the hydrocarbon vinyl compound is preferably 100 to 50: 0 to 50 (mol%), more preferably 100 to 70: 0 to 30 (mol%).
In addition, a random polymer and a block polymer are contained in said copolymer.
The vinyl ether compound polymer or copolymer described above usually has a terminal acetal group or the like, but if it is a polymer from which this has been removed, it becomes a more stable polymer. A polymer from which the terminal acetal group and the like have been removed can be obtained by hydrogenating the above polymer.
[0065]
The method for producing the polymer is not particularly limited, but it can be efficiently produced by polymerizing by the method described in the above-mentioned [Production of Polymer] and hydrogenating as necessary. Can be manufactured.
As a typical example of the polymer or copolymer of the vinyl ether compound, the structural unit represented by the general formula (3), or the structural unit represented by the general formula (3) and the general formula (4). The polymer whose terminal of the polymer is general formula (5) or (6) and general formula (7) or (8) is mentioned.
[0066]
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[0067]
(Wherein R^Five~ R⁷Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R⁸Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R⁹Is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R^Five~ R⁹May be the same or different for each structural unit, and R⁸When there are a plurality of O, a plurality of R⁸O may be the same or different. )
[0068]
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[0069]
(Wherein R¹~ R^FourRepresents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. )
[0070]
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[0071]
(Wherein R^Five~ R⁹And p are the same as those in the general formula (2))
[0072]
Embedded image

[0073]
(Wherein R¹~ R^FourIs the same as in the general formula (4))
[0074]
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[0075]
(Wherein R^Five~ R⁹And p are the same as those in the general formula (3))
[0076]
Embedded image

[0077]
(Wherein R¹~ R^FourIs the same as in the general formula (4))
Among them, the structural unit is represented by the general formula (3), and the terminal of the polymer is a polymer represented by the general formula (5) and the general formula (7). The general formulas (3), (5) and P in (7) is 0 and R⁹Is an ethyl group and p is 0 and R⁹Is a isopropyl group or an isobutyl group, and a polymer having a ratio of 100 to 50: 0 to 50 (molar ratio), more preferably 100 to 70: 0 to 30 is particularly preferably used.
[Application of polymer to lubricating oil for refrigerators]
The said polymer can be utilized for various uses. For example, it is useful for solvents, lubricants, adhesives, resins, etc., and a polymer having a molecular weight more than 3 times the molecular weight corresponding to the main component is more fluid and stable than a polymer of 1% by weight or more. There is an effect of improving the performance and the inherent performance.
[0078]
In particular, the polymer is effective as a lubricating oil for refrigerators, and the solubility with hydrofluorocarbon (HFC) as a refrigerant is remarkably improved. The same applies when the refrigerant is ammonia, hydrocarbon, carbon dioxide, or the like.
Therefore, as a refrigerant used in a refrigerator to which the polymer of the present invention is applied, hydrofluorocarbon, fluorocarbon, hydrocarbon, ether, carbon dioxide or ammonia refrigerant is used. Among these, examples of the hydrofluorocarbon refrigerant include 1,1,1,2-tetrafluoroethane (R134a), difluoromethane (R32), pentafluoroethane (R125), and 1,1,1-trifluoroethane (R143a). These may be used alone or in combination of two or more. Examples of the mixed refrigerant include a mixture of R32, R125, and R134a in a weight ratio of 23:25:52 (hereinafter referred to as R407C), a mixture of a weight ratio of 25:15:60, and a weight of R32 and R125. A 50:50 mixture (hereinafter referred to as R410A), a R32 and R125 weight ratio of 45:55 (hereinafter referred to as R410B), a R125, R143a, and R134a weight ratio of 44: 52: 4. (Hereinafter referred to as R404A), a mixture of R125 and R143a in a weight ratio of 50:50 (hereinafter referred to as R507), and the like.
[0079]
【Example】
The present invention will be further described in detail using examples.
The test methods used in the examples are as follows.
[Measurement method of molecular weight distribution]
The weight average molecular weight and the number average molecular weight were determined from the elution curve by high performance liquid chromatography (high speed GPC), and the weight average molecular weight / number average molecular weight was calculated as the molecular weight distribution. The measurement conditions are as follows.
[0080]
Column: TSK G3000H8 + G2000H8 + G1000H8
Mobile phase: Special grade THF
Flow rate: 1.4ml / min
Sample dissolution method: Dissolved in mobile phase solvent (sample concentration 2 mg / ml)
Sample injection volume: 400 μl
Detector: RI (differential refraction) detector, cell temperature 40 ° C.
Standard data for preparing calibration curves: Polyethylene glycol and polystyrene
[Measurement of two-layer separation temperature]
0.45 g of a sample was weighed into a pressure-resistant glass ampoule, and this was connected to a vacuum pipe and a hydrofluorocarbon mixed refrigerant (R410A) pipe. After the ampule was vacuum degassed at room temperature, 2.55 g of R410A refrigerant was collected in liquid form. Subsequently, the ampule was sealed, and it cooled gradually from room temperature to -50 degreeC in the thermostat, and measured the temperature which layer separation begins.
[Comparative Example 1]
After charging 2248 g of ethyl alcohol, 402 g of isobutyl alcohol, 21.4 g of boron trifluoride diethyl ether complex and 15.2 liter of isononane in a 100 liter reaction vessel, the reaction temperature was maintained at 45 ° C. To this reaction vessel, a mixture of 41.5 kg of ethyl vinyl ether and 6.4 kg of isobutyl vinyl ether was continuously fed for 5 hours. The molecular weight distribution curve by GPC of the polymer obtained is such that the molecular weight 920 is the maximum value of the peak strength, and the molecular weight is not less than the maximum molecular weight × 3 (= 2760) of the peak strength. The polymer was 1.58%.
[Example 1]
Comparative Example 1 except that instead of the mixture of ethyl vinyl ether and isobutyl vinyl ether of Comparative Example 1, a mixture containing 1000 ppm (48 g) of ethanol was further continuously fed to the mixing section. Polymerization was carried out in the same manner as above.
[0081]
The molecular weight distribution curve by high-speed GPC of the obtained polymer is such that the molecular weight 910 is the maximum value of peak strength, and the molecular weight is the maximum value of peak strength × 3 (= 2730) or more. The polymer was 0.81%. The molecular weight distribution was 1.18.
[Comparative Example 2]
Ethyl alcohol 26kg, isobutyl alcohol 5kg, boron trifluoride diethyl ether complex 250g and toluene 379kg 3m^ThreeThen, the reaction temperature was kept at 25 ° C. To this reaction vessel, a mixture of 520 kg of ethyl vinyl ether and 80 kg of isobutyl vinyl ether was continuously supplied for 8 hours. The molecular weight distribution curve by high-speed GPC of the polymer obtained is such that the molecular weight is 780 and the peak strength is the maximum value, and the molecular weight is the maximum value of the peak strength × 3 (= 2340) or more. The polymer was 1.33%.
[Example 2]
While the mixture of ethyl vinyl ether and isobutyl vinyl ether is continuously supplied under the production conditions of Comparative Example 2, the ethanol is heated to 60 ° C. while stirring the gas phase portion of the reactor with a stirring blade. The polymer was produced by supplying it to the gas phase part at a rate of 200 g / hr together with the nitrogen gas. The molecular weight distribution was 1.19.
[0082]
The molecular weight distribution curve of the polymer obtained by high-speed GPC is such that the molecular weight is 750 and the peak strength is the maximum value, and the molecular weight is the maximum value of the peak strength × 3 (= 2250) or more. The polymer was 0.68%.
[Comparative Example 3]
60 ml of water-containing toluene (water content 350 ppm) and 1.0 g of boron trifluoride diethyl ether complex were placed in a 200 ml four-necked flask and maintained at a reaction temperature of 25 ° C. Thereto, 41.7 g of styrene was continuously fed over about 45 minutes for polymerization. The molecular weight distribution curve by high-speed GPC of the obtained polymer is such that the molecular weight 3730 is the maximum value of peak strength, and the molecular weight is the maximum value of peak strength × 3 (= 11190) or more. The polymer was 4.10%.
Example 3
Instead of the styrene of Comparative Example 3, a mixture of 300 ppm (0.04 g) of ethanol added to styrene was supplied to produce a polymer. The molecular weight distribution curve by high-speed GPC of the obtained polymer is such that the molecular weight 3330 is the maximum value of the peak strength, and the molecular weight is the maximum value of the peak strength × 3 (= 9990) or more. The polymer was 2.93%. The molecular weight distribution was 2.20.
[Examples 4 and 5 and Comparative Examples 4 and 5]
The polymers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were hydrogenated, and the two-layer separation temperature of the hydride for refrigerant R410A was measured. The measurement results are shown in Table 1.
[0083]
The hydrogenation method was performed as follows.
Catalyst adjustment
A 2 liter autoclave made of SUS316L was charged with 12 g of nickel diatomaceous earth catalyst (product of NGC, product N113) and 300 g of isooctane. After replacing the inside of the autoclave with nitrogen and then with hydrogen, the hydrogen pressure was 30 kg / cm.²The temperature was raised to G, the temperature was maintained at 140 ° C. for 30 minutes, and then cooled to room temperature. After replacing the inside of the autoclave with nitrogen, 20 g of acetaldehyde diethyl acetal was added to the autoclave, followed by nitrogen substitution again, and after hydrogen substitution, the hydrogen pressure was 30 kg / cm.²The temperature was raised as G. After maintaining at 130 ° C. for 30 minutes, it was cooled to room temperature. While the pressure inside the autoclave increased as the temperature rose, a decrease in the hydrogen pressure was observed due to the reaction of acetaldehyde diethyl acetal. Pressure decreases, 30 kg / cm²When G or less, add hydrogen and add 30kg / cm²G. The pressure was reduced to room temperature, then the inside of the autoclave was replaced with nitrogen and then the pressure was released.
[0084]
Hydrogenation of vinyl ether polymers
The catalyst-containing autoclave obtained by the above catalyst preparation was opened, the liquid layer was removed by decantation, and 400 g of the polymer obtained in Example 1 was added. After replacing the inside of the autoclave with nitrogen and then with hydrogen, the hydrogen pressure was 30 kg / cm.²The temperature was raised to G. After holding at 140 ° C. for 2 hours, the mixture was cooled to room temperature. While the pressure inside the autoclave increased as the temperature rose, a decrease in hydrogen pressure was observed as the reaction proceeded. When the pressure decreases, hydrogen is added in a timely manner and the inside of the autoclave is 30 kg / cm.²G. The inside of the autoclave was purged with nitrogen and then depressurized. The reaction solution was recovered, 100 g of isooctane was added, and the catalyst was removed by filtration. The filtrate was subjected to vacuum treatment with a rotary evaporator to remove the solvent and light components, and a sample of Example 4 was obtained.
[0085]
In the same manner, samples of Example 5, Comparative Example 4 and Comparative Example 5 were obtained from the polymers of Example 2, Comparative Example 1 and Comparative Example 2.
[0086]
[Table 1]

[0087]
【The invention's effect】
(1) In a method for producing a polymer in which a polymer is polymerized while sequentially supplying monomers in the presence of a catalyst, when the polymer is produced by sequentially supplying a chain transfer agent, the polymer has a narrow molecular weight distribution and is sharp. become.
(2) The polymer is a polymer or copolymer of a polyvinyl ether compound, the polymer has a weight average molecular weight of 300 to 50,000, and corresponds to the maximum peak strength of the molecular weight distribution curve The refrigerating machine lubricating oil mainly composed of a polymer having a molecular weight of 3 times or more of the molecular weight to be 1% by weight or less of the total polymer has high solubility in the refrigerant.
[Brief description of the drawings]
FIG. 1 GPC molecular weight of a polymer obtained by the polymerization method of the present invention
It is a conceptual diagram of a distribution curve.
[Explanation of symbols]
(1) The molecular weight point corresponding to the maximum peak intensity of the molecular weight distribution curve
(2) The peak intensity of the molecular weight distribution curve is three times the molecular weight corresponding to the maximum value.
Molecular weight point

Claims (7)

In the method for producing a polymer in which cationic polymerization is performed while sequentially supplying monomers in the presence of a catalyst including a polymerization catalyst and a polymerization initiator, the chain transfer agent is sequentially supplied, and the following (1) to (3) are satisfied: a method of manufacturing a to polymer, to vaporize chain transfer agent, supplied to the gas phase of the reaction system, the production method of the polymer.
(1) The supply amount of the chain transfer agent that is sequentially supplied is 0.02 to 1.0% by weight with respect to the monomer.
(2) The input amount of the polymerization initiator is 1/10000 to 1/2 (mole) of the total monomer amount.
(3) The input amount of the polymerization catalyst is 1/600 to 1/30 (mol) of the polymerization initiator. The method for producing a polymer according to claim 1, wherein the period from the start of supply of the chain transfer agent to the end of supply is a period of ½ or more of the monomer supply period. The method for producing a polymer according to claim 1 or 2 , wherein the monomer is one or more compounds selected from hydrocarbon-based vinyl compounds represented by the general formula (1).

(Wherein, R ¹ to R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.) The method for producing a polymer according to claim 1 or 2 , wherein the monomer is one or more compounds selected from vinyl ether compounds represented by the general formula (2).

(In the formula, R ^{5 to} R ⁷ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ⁸ is a divalent hydrocarbon having 1 to 10 carbon atoms. A hydrocarbon group, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R ^{5 to} R ⁹ may be the same or different for each structural unit, in the case where R ⁸ O is plural, plural R ⁸ O may be the same or different.) One or more compounds selected from vinyl ether compounds represented by the general formula (2) and one type selected from hydrocarbon-based vinyl compounds represented by the general formula (1) Alternatively, the method for producing a polymer according to claim 1 or 2 , wherein the polymer is two or more compounds.

(In the formula, R ^{5 to} R ⁷ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ⁸ is a divalent hydrocarbon having 1 to 10 carbon atoms. A hydrocarbon group, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, p is an average value of 0 to 10 and R ^{5 to} R ⁹ may be the same or different for each structural unit, in the case where R ⁸ O is plural, plural R ⁸ O may be the same or different.)

(Wherein R ^{1 to} R ⁴ represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms.) The weight average molecular weight of the polymer is 300 to 50,000, the weight of any of claims 1 to 5 molecular weight distribution of the polymer ([weight average molecular weight) / (number-average molecular weight]) is 2.5 or less Manufacturing method of coalescence. It claims 1-6 content of the polymer having 3 or more times the molecular weight of the molecular weight corresponding to the maximum value of the click intensity is less than 1% by weight of the total polymer - peak in the molecular weight distribution curve of the polymer The manufacturing method of the polymer as described in any one of.

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