JP3937830B2 - Catalyst for polymerization of oxirane compound, and method for producing oxirane compound polymer using the catalyst - Google Patents

Description

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５は、互いに同一であっても異なっていてもよく、水素原子または低級アルキル基である。）
【化５】

（式中、ｎは２から１０の整数である。）
【００１０】
また、本発明によるオキシラン化合物重合体の製造方法は、上記特徴を有する触媒の存在下に単量体オキシラン化合物をその重合体が不溶な有機溶媒中で懸濁析出重合せしめ、オキシラン化合物の重合体を製造する方法である。
【００１１】
以下、本発明の構成につき詳細に説明する。
【００１２】
本発明による触媒において使用されるアルキルアルミニウム化合物は、
一般式
（Ｒ_７ ）_ｐ ＡｌＸ_３−ｐ
（式中、Ｒ_７ は低級アルキル基、例えば炭素数１〜６のアルキル基、Ｘはハロゲン原子または水素原子、ｐは１、１．５、２または３である。）
で示される化合物である。
【００１３】
アルキルアルミニウム化合物としては、例えばトリエチルアルミニウム、ジエチルアルミニウムクロライド、エチルアルミニウムセスキクロライド［Ｅｔ_３ Ａｌ_２ Ｃｌ_３ ］、トリイソブチルアルミニウム、ジイソブチルアルミニウムハイドライド、トリ−ｎ−ブチルアルミニウム、トリ−ｎ−プロピルアルミニウム等を挙げることができ、これらは用いられる単量体オキシラン化合物に応じてそれぞれ単独で、または２種以上の組み合わせで用いることができる。
【００１４】
また、本発明による触媒において使用される燐のオキソ酸化合物は、燐酸、一般式［ II ］で示されかつＨ _３ Ｐ０ _４ 相当で９０〜１１０重量％（Ｈ _３ Ｐ０ _４ 相当で１００重量％を越えるものは、通常、縮合燐酸と呼ばれる）であるポリ燐酸の混合物、または酸性燐酸エステルである。
燐のオキソ酸化合物としてポリ燐酸の混合物を用いると、得られる触媒のオキシラン化合物に対する重合活性が大きくなり好ましい。
アルコール類と燐酸との部分エステル化物である酸性燐酸エステル類は、一般式
Ｏ＝Ｐ（ＯＲ_８）_ｑ ＯＨ）_３−ｑ
（式中、Ｒ_８は低級アルキル基、例えば炭素数１〜６のアルキル基、ｑは１または２である。）
で示される化合物であり、酸性燐酸メチル、酸性燐酸エチル、酸性燐酸プロピル、酸性燐酸イソプロピル、酸性燐酸ブチルを例示することができる。
【００１６】
該燐酸、またはポリ燐酸の混合物中に水分が少量存在していても問題はないが、燐酸、またはポリ燐酸の混合物中の水分が多量であると触媒反応を阻害し、重合活性が低下する傾向があるので、本発明においてはＨ_３ ＰＯ_４ 相当で好ましくは８３重量％以上、より好ましくは９０重量％以上の燐酸、またはポリ燐酸の混合物を用いる。
【００１７】
本発明による触媒は、一般式［Ｉ］で示されるアルキル置換ピリジンを含むものである。したがって、触媒活性が高く、また、得られるオキシラン化合物重合体の分子量も大きくなり好ましい。
【００１８】
一般式［Ｉ］中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５は、互いに同一であっても異なっていてもよく、水素原子または低級アルキル基、例えば炭素数１〜６のアルキル基である。
【００１９】
一般式［Ｉ］で示されるアルキル置換ピリジンとしては、２，４，６−トリメチルピリジン、２，３，６−トリメチルピリジン、２，４−ジメチルピリジン、２，５−ジメチルピリジン、２，６−ジメチルピリジン、３，５−ジメチルピリジン、４−メチルピリジン、３−エチル−６−メチルピリジン、４−イソプロピルピリジン、２−プロピルピリジン、２，３，５，６−テトラメチルピリジン等を挙げることができる。好ましいアルキル置換ピリジンは、少なくとも２位および／または６位がアルキル置換されたピリジンである。特に好ましい化合物は２，４，６−トリメチルピリジンである。
【００２０】
上記アルキルアルミニウム化合物、燐のオキソ酸化合物、および含窒素環状化合物を反応させて本発明の触媒を合成する際、アルキルアルミニウムと燐のオキソ酸化合物の割合は、燐のオキソ酸化合物が分子内に持つＯＨ基（オキソ酸化合物が水を含む場合はオキソ酸化合物のＯＨ基と水のＯＨ基の総和）のモル数に依存し、該ＯＨ基１モルに対してアルキルアルミニウム化合物０．６５〜０．９５モル、好ましくは０．７〜０．９３モルの範囲内にある。この割合が上記範囲を出ると、懸濁析出重合に用いた際に、重合体が反応槽の壁に付着する量が増加するので好ましくない。
含窒素環状化合物の割合は、アルキルアルミニウム化合物１モルに対して好ましくは０．０１〜０．５モル、より好ましくは０．０３〜０．２５モルである。含窒素化合物の割合がこの範囲を外れると、得られる触媒のオキシラン化合物に対する重合活性が低下する傾向がある。
【００２１】
これら三つの原料物質の反応順序は特に限定されるものではなく、まずアルキルアルミニウム化合物と燐のオキソ酸化合物とを反応させ、その後この反応生成物に含窒素環状化合物を反応させてもよいし、また、まずアルキルアルミニウム化合物と含窒素環状化合物を反応させ、その後この反応生成物に燐のオキソ酸化合物を反応させてもよく、得られた触媒のオキシラン化合物に対する重合活性に大きな差はない。上記各反応の反応温度は、用いられるアルキルアルミニウム化合物あるいは燐のオキソ酸化合物によって適宜選択されるが、通常−２０℃〜１２０℃の範囲内にある。触媒合成の反応は窒素ガス等の不活性ガス雰囲気下で無溶媒あるいは不活性溶媒中で行うのが好ましい。不活性溶媒は特に限定されるものではないが、例えばヘキサン、ヘプタン、シクロヘキサン、オクタン等の脂肪族炭化水素類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ジエチルエーテル、ジプロピルエーテル、メチルブチルエーテル、ジメトキシエタン等のエーテル類等を挙げることができ、これらが単独であるいは２種以上の混合溶媒として用いられる。
【００２２】
上記アルキルアルミニウム、燐のオキソ酸化合物、および含窒素環状化合物の反応により得られた触媒は、オキシラン化合物の懸濁析出重合に非常に適している。重合せしめ得るオキシラン化合物としては、例えば、エチレンオキシド、プロピレンオキシド、ブテンオキシド、イソブチレンオキシド、ブタジエンモノオキシド等のアルキレンオキシド類；エピクロルヒドリン、エピブロムヒドリン、メタクリルクロリドオキシド、トリフルオロメチルエチレンオキシド、ジクロロイソブチレンオキシド、スチレンオキシド等の置換アルキレンオキシド類；シクロヘキセンオキシド、ビニルシクロヘキセンオキシド等の脂環状エポキシド類；アリルグリシジルエーテル、フェニルグリシジルエーテル、クロロエチルグリシジルエーテル、メチルグリシジルエーテル、２−メトキシエチルグリシジルエーテル、２−（２−メトキシエトキシ）エチルグリシジルエーテル、シクロヘキシルグリシジルエーテル、ベンジルグリシジルエーテル等のグリシジルエーテル類；グリシジルアクリレート、グリシジルメタクリレート等のグリシジルエステル類等を挙げることができる。これらのうち、下記一般式［III］ で示されるオキシラン化合物の単独重合あるいは２種以上の共重合を行うと、重合速度が速く、また得られる重合体の分子量が大きくなり好ましい。
【００２３】
【化６】

（式中、ｍは０または１である。Ｒ_６ は水素原子、置換基を有していてもよいアルキル基、シクロアルキル基、フェニル基、アラルキル基、アルケニル基または（メタ）アクリロイル基であり、該置換基はハロゲン、メトキシ基、エトキシ基またはメトキシエトキシ基である。）
【００２４】
本発明による重合方法は、上記触媒の存在下に、単量体に対し不活性でありかつ得られる重合体を溶解しない有機溶媒中で、単量体オキシラン化合物を懸濁析出重合せしめて、オキシラン化合物の重合体を製造する方法である。
【００２５】
単量体は有機溶媒に対して可溶であっても不溶であってもよいが、少なくとも一部は可溶である方が好ましい。このような溶媒の例としてはヘキサン、ヘプタン、シクロヘキサン、オクタン等の脂肪族炭化水素類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ジエチルエーテル、ジプロピルエーテル、メチルブチルエーテル、ジメトキシエタン等のエーテル類等を挙げることができ、用いられるオキシラン化合物の種類および重合温度に応じて適宜選択される。好ましくは脂肪族炭化水素類が用いられる。
【００２６】
単量体オキシラン化合物、有機溶媒および触媒の混合割合は、通常、オキシラン化合物の１００重量部に対し、有機溶媒１００〜１０００重量部、触媒０．０１〜５重量部の範囲内にあることが好ましい。重合温度は特に限定されるものではないが、通常−２０℃から１５０℃の範囲内にあり、触媒の活性、用いられる有機溶媒およびオキシラン化合物の種類に応じて適宜選択される。また、重合は通常撹拌下で行われる。
【００２７】
【発明の実施の形態】
本発明を実施するための具体的な形態を以下に実施例を挙げて説明する。但し、本発明はその要旨を逸脱しない限り以下の実施例に限定されるものではない。
［実施例１］
内部を窒素置換した容量３００ｍｌのガラス製フラスコに、トリイソブチルアルミニウム３９ｍｌを投入し、ついでヘキサン８１ｍｌを加え、全体を撹拌した。燐酸（Ｈ_３ ＰＯ_４ １００重量％相当）６．０８ｇをジエチルエーテル１８０ｍｌに溶解してなる溶液を、反応温度を５℃前後に温度調節しながら、トリイソブチルアルミニウムのヘキサン溶液中へ撹拌下に徐々に加え、両者を反応させた（燐酸の添加割合は、燐酸のＯＨ基１モルに対してトリイソブチルアルミニウム０．８３モルに相当する）。この反応液に含窒素環状化合物として２，４，６−トリメチルピリジン（ｐＫａ＝７．４３）１．５ｍｌを撹拌下に加え、６０℃で１時間撹拌を続けた。こうして触媒を調製した。
【００２８】
内部を窒素置換した容量２０リットルのステンレス製反応槽にエピクロルヒドリン１．８リットルとヘキサン９リットルを入れ、ここに上記触媒全量を添加して、全体を２０℃で撹拌しながら６時間重合反応を行った。反応槽内には直径１ｍｍ程度の粒子状の重合体が析出した。反応槽の壁に付着した重合体の量は２．８％であった。なお、重合体の反応槽壁付着量は下記の式により算出した：
【式１】

【００２９】
［実施例２］
含窒素環状化合物として、２，４−ジメチルピリジン（ｐＫａ＝６．７４）１．５ｍｌを用いた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１ｍｍ程度の粒子状の重合体が析出した。壁付着量は３．６％であった。
【００３１】
［実施例３］
燐酸（Ｈ_３ＰＯ_４ １００重量％相当）の添加量を７．２４ｇ（燐酸のＯＨ基１モルに対してトリイソブチルアルミニウム０．７０モルに相当する）とした点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．５ｍｍ程度の粒子状の重合体が析出した。壁付着量は４．８％であった。
【００３２】
［実施例４］
燐酸（Ｈ_３ＰＯ_４ １００重量％相当）の添加量を５．４７ｇ（燐酸のＯＨ基１モルに対してトリイソブチルアルミニウム０．９３モルに相当する）とした点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．０ｍｍ程度の粒子状の重合体が析出した。壁付着量は６．１％であった。
【００３３】
［実施例５］
燐のオキソ酸化合物として、燐酸の部分エチルエステル化物である酸性燐酸エチル（燐含有量２１重量％）２１ｇ（酸性燐酸エチルのＯＨ基１モルに対してトリイソブチルアルミニウム０．８３モルに相当する）を用いた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．５ｍｍ程度の粒子状の重合体が析出した。壁付着量は５．９％であった。
【００３４】
［実施例６］
燐のオキソ酸化合物として、燐酸を水溶液形態で（Ｈ_３ＰＯ_４ ８５重量％相当）５．４ｇ（燐酸のＯＨ基と水のＯＨ基の総和１モルに対してトリイソブチルアルミニウム０．８３モルに相当する）用いた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１ｍｍ程度の粒子状の重合体が析出した。壁付着量は５．９％であった。
【００３５】
［実施例７］
アルキルアルミニウム化合物として、トリエチルアルミニウム３７ｍｌを用い、これに燐酸（Ｈ_３ＰＯ_４ １００重量％相当）１０．７ｇ（燐酸のＯＨ基１モルに対してトリエチルアルミニウム０．８３モルに相当する）と、２，４，６−トリメチルピリジン２．７ｍｌとを加えた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．５ｍｍ程度の粒子状の重合体が析出した。壁付着量は４．８％であった。
【００３６】
［実施例８］
実施例１と同様の手順で触媒を調製し、次いでオキシラン化合物として、エピクロルヒドリン１．５リットルおよびエチレンオキシド０．６リットルを用いた点を除いて、実施例１と同様の手順で重合反応を行った。反応槽内には直径１ｍｍ程度の粒子状の共重合体が析出した。壁付着量は４．１％であった。
【００３７】
［実施例９］
実施例１と同様の手順で触媒を調製し、次いでオキシラン化合物として、プロピレンオキシド０．８リットル、エチレンオキシド０．９リットルおよびアリルグリシジルエーテル１２０ｍｌを用いた点を除いて、実施例１と同様の手順で重合反応を行った。反応槽内には直径１ｍｍ程度の粒子状の三元共重合体が析出した。壁付着量は４．９％であった。
【００３８】
［実施例１０］
実施例１と同様の手順で触媒を調製し、次いでオキシラン化合物として、スチレンオキシド１．８リットルを用いた点を除いて、実施例１と同様の手順で重合反応を行った。反応槽内には直径１．５ｍｍ程度の粒子状の重合体が析出した。壁付着量は６．３％であった。
【００３９】
［比較例１］
燐酸（Ｈ_３ ＰＯ_４ １００重量％相当）の添加量を５．０７ｇ（燐酸のＯＨ基１モルに対してトリイソブチルアルミニウム１．００モルに相当する）とした点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．０ｍｍ程度の粒子状の重合体が析出した。壁付着量は１２．４％であった。
【００４０】
［比較例２］
燐酸（Ｈ_３ ＰＯ_４ １００重量％相当）の添加量を８．４５ｇ（燐酸のＯＨ基１モルに対してトリイソブチルアルミニウム０．６０モルに相当する）とした点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１．５ｍｍ程度の粒子状の重合体が析出した。壁付着量は１６．８％であった。
【００４１】
［比較例３］
含窒素環状化合物として、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ｐＫａ＝１２．５）１．５ｍｌを用いた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径８ｍｍ程度の大きな粒状の重合体が析出した。壁付着量は１８．５％であった。
【００４２】
［比較例４］
含窒素環状化合物として、２−エチルピリジン（ｐＫａ＝５．８９）１．５ｍｌを用いた点を除いて、実施例１と同様の手順で触媒を調製し、これを用いて重合反応を行った。反応槽内には直径１５ｍｍ程度の大きな粒状の重合体が析出した。壁付着量は２６．２％であった。
【００４３】
［重合体の評価］
得られた重合体（反応槽壁付着物も含む）を充分に真空乾燥し、重量を測定して重合体収率を求めた。また、得られた重合体を真空乾燥した後ジメチルホルムアミドに溶解し、ゲルパーミエーションクロマトグラフィー法で重合体の分子量を求め、さらに標準ポリスチレン換算で重量平均分子量を算出した。これらの評価結果を表１に示す。
【００４４】
【表１】

【００４５】
析出した重合体の様相から明らかなように、実施例１〜７で得られた触媒を用いてエピクロルヒドリンの重合を行うと、細かな粒子状の単独重合体が得られ、かつ壁付着量も少なくなっている。また、表１から明らかなように、これら実施例では重合体収率、得られた重合体の分子量が共に高い数値を示した。異種の単量体を用いて（共）重合を行った実施例８〜１０ではいずれも少ない壁付着量で粒子状の重合体が得られ、これらの実施例でも重合体収率、得られた重合体の分子量は共に高い数値を示した。
【００４６】
これに対し、オキソ酸化合物のＯＨ基１モルに対するアルキルアルミニウムの値が０．６５〜０．９５モルの範囲を外れる比較例１、比較例２では、粒子状の重合体が得られるものの、壁付着量が多くなっている。１，８−ジアザビシクロ［５，４，０］−７−ウンデセンを用いた比較例３、および２−エチルピリジンを用いた比較例４では、重合体収率、重合体の分子量はかなり高いが、重合体は大きな粒状となって得られ、これら化合物は懸濁析出重合用触媒には適しないことが分かる。
【００４７】
【発明の効果】
本発明によるオキシラン化合物の重合用触媒は、以上のように構成されており、これを用いることによって高い生産効率で高分子量の重合体が得られ、かつ、反応槽壁への重合体の付着量が少ない。したがって、本発明による触媒を用いれば、自動車用ゴム部品、電気、電子機器用ゴム部材、各種プラスチックブレンド用ポリマー、高分子固体電解質等の非常に広範な分野で使用されている高品質のオキシラン化合物重合体を効率よくかつ容易に製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymerization catalyst suitable for producing a polymer of an oxirane compound such as ethylene oxide, epichlorohydrin, and allyl glycidyl ether by suspension precipitation polymerization, and to a method for producing a polymer of an oxirane compound using the polymerization catalyst. .
[0002]
[Prior art]
The polymer of the oxirane compound becomes a polymer having various properties by selecting the type of the oxirane compound used as a raw material. Therefore, rubber components for automobiles, rubber members for electric and electronic devices, polymers for various plastic blends, It is used in a very wide range of fields such as molecular solid electrolytes.
[0003]
Industrial production methods for oxirane compound polymers include solution polymerization in which the oxirane compound is polymerized in an organic solvent in which the monomer and polymer are soluble, and polymerization of the oxirane compound in an organic solvent in which the polymer is insoluble. Suspension precipitation polymerization in which a particulate polymer is precipitated is known. Among these, the latter polymerization method has the advantage that the monomer concentration can be increased at the time of polymerization, and separation of the polymer after polymerization and the solvent is easy, but it is necessary to select a specific catalyst and solvent. There is.
[0004]
As catalysts capable of polymerizing oxirane compounds, those having the action of Lewis acids such as boron fluoride, aluminum chloride, tin chloride and iron chloride are known. When polymerization is performed using these catalysts, a polymer having a relatively low molecular weight (for example, a molecular weight of several thousand to several tens of thousands) can be obtained.
[0005]
In order to obtain a high molecular weight polymer useful in a specific field such as rubber industry, a reaction product of alkylzinc and water, a reaction product of organotin compound and phosphate ester, a reaction product of alkylaluminum and water It is known to use a reaction product of an alkylaluminum and a phosphoric acid compound. In particular, as a catalyst using alkylaluminum, a catalyst obtained by adding a chelating agent such as acetylacetone to a reaction product of alkylaluminum and water (for example, J. Polym. Sci. A-1, 7, 525 (1969 )), A catalyst obtained by adding a third component comprising an amine compound, an organic phosphorus compound and / or an organic arsenic compound to the reaction product of an alkylaluminum and a phosphoric acid compound (see Japanese Patent Publication No. 46-27534), A catalyst obtained by adding an N-substituted morpholine such as N-ethylmorpholine to a reaction product of an alkylaluminum and a phosphoric acid compound (see Japanese Examined Patent Publication No. 56-8852), or 1,8-diazabicyclo [ The catalyst added with 5,4,0] -7-undecene (see Japanese Patent Publication No. 56-51171) was excellent in obtaining a high molecular weight oxirane compound polymer. It has been proposed as a catalyst. As a catalyst for obtaining a high molecular weight oxirane compound polymer by suspension precipitation polymerization, the present inventors previously used an amine compound having a specific pKa value as a reaction product of an alkylaluminum and phosphorus oxoacid compound. An added catalyst was proposed (Japanese Patent Application No. 2000-193798). The present invention is an extension of this prior invention and is intended to further improve production efficiency.
[0006]
[Problems to be solved by the invention]
However, most of the prior art relating to the catalyst using the alkylaluminum is based on solution polymerization. When suspension precipitation polymerization of an oxirane compound is performed in the presence of these catalysts, a high molecular weight polymer may be obtained in some cases. There is a problem that the polymer cannot be obtained or the precipitated polymer is solidified without becoming particles, so that stirring cannot be performed in the reactor, and the polymer cannot be taken out from the reactor.
[0007]
An object of the present invention is a method by which a high molecular weight oxirane compound polymer can be produced more effectively and with higher production efficiency by further improving a catalyst using an alkylaluminum suitable for suspension precipitation polymerization. Is to provide.
[0008]
[Means for Solving the Problems]
The inventors of the present invention have made various studies in order to solve the above problems. As a result, a catalyst in which a specific alkyl-substituted pyridine is further added as a third component to the reaction product of an alkylaluminum compound and a phosphorus oxoacid compound. Only when the aluminum and phosphorus oxo acid compounds are in a specific ratio, the adhesion of the polymer to the reaction vessel wall during suspension precipitation polymerization is remarkably reduced and the production efficiency is improved, and the present invention is completed. It came.
[0009]
The catalyst for oxirane compound polymerization according to the present invention is a catalyst that can significantly reduce the adhesion of the polymer to the reaction vessel wall when the oxirane compound is suspended and precipitated in an organic solvent insoluble in the polymer. (A) an alkylaluminum compound, (B) a phosphorus oxoacid compound having at least one OH group in the molecule, and (C) an alkyl-substituted pyridine represented by the following general formula [I]: A) The ratio of the alkylaluminum compound and (B) the phosphorus oxo acid compound having at least one OH group in the molecule is the OH group of the oxo acid compound (or the OH group of the oxo acid compound if the oxo acid compound contains water). the sum of OH groups of water) in the range of alkylaluminum 0.65-0.95 mol relative to 1 mol, (B) an oxo acid compound of phosphorus, phosphoric acid, the following general formula [II It is characterized in that in shown and H ₃ PO ₄ mixture corresponding in a 90 to 110 wt% polyphosphoric acid, or an acidic phosphoric ester.
[Formula 4]

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different from each other, and are a hydrogen atom or a lower alkyl group.)
[Chemical formula 5]

(Where n is an integer from 2 to 10)
[0010]
In addition, the method for producing an oxirane compound polymer according to the present invention comprises subjecting a monomer oxirane compound to suspension precipitation polymerization in an organic solvent in which the polymer is insoluble in the presence of the catalyst having the above-described characteristics, and It is a method of manufacturing.
[0011]
Hereinafter, the configuration of the present invention will be described in detail.
[0012]
The alkylaluminum compound used in the catalyst according to the invention is
Formula _{(R 7) p AlX 3-} p
(Wherein R ₇ is a lower alkyl group such as an alkyl group having 1 to 6 carbon atoms, X is a halogen atom or a hydrogen atom, and p is 1, 1.5, 2 or 3.)
It is a compound shown by these.
[0013]
The alkyl aluminum compounds, for example triethylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride _{[Et 3 Al 2 Cl 3]} , triisobutylaluminum, diisobutylaluminum hydride, tri -n- butyl aluminum, tri -n- propyl aluminum These may be used alone or in combination of two or more depending on the monomer oxirane compound used.
[0014]
Also, oxo acid compound of phosphorus used in the catalyst according to the present invention, phosphoric acid, represented by the general formula [II] and _H 3 P0 ₄ equivalent with 90 to 110 _{wt% (H} 3 P0 ₄ 100% by weight equivalent to Beyond are mixtures of polyphosphoric acid, usually called condensed phosphoric acid), or acidic phosphoric esters.
When a mixture of polyphosphoric acid is used as the phosphorus oxoacid compound, the polymerization activity of the resulting catalyst with respect to the oxirane compound is preferably increased.
Alcohol and acid phosphate ester is a partial ester of phosphoric acid represented by the general formula _{O = P (OR 8) q} OH) 3-q
(In the formula, R ₈ is a lower alkyl group such as an alkyl group having 1 to 6 carbon atoms, and q is 1 or 2.)
In a compound represented, acid phosphate methyl, acid phosphate ethyl, acid phosphate propyl, acid phosphate isopropyl, Ru can be exemplified acid phosphate butyl.
[0016]
There is no problem even if a small amount of water is present in the phosphoric acid or polyphosphoric acid mixture, but if the amount of water in the phosphoric acid or polyphosphoric acid mixture is large, the catalytic reaction tends to be inhibited and the polymerization activity tends to decrease. Therefore, in the present invention, a phosphoric acid or a mixture of polyphosphoric acid equivalent to H ₃ PO ₄ and preferably 83% by weight or more, more preferably 90% by weight or more is used.
[0017]
The catalyst according to the present invention contains an alkyl-substituted pyridine represented by the general formula [I]. Therefore, the catalyst activity is high, and the molecular weight of the obtained oxirane compound polymer is preferably increased.
[0018]
In general formula [I] , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same as or different from each other, and may be a hydrogen atom or a lower alkyl group such as an alkyl having 1 to 6 carbon atoms. It is a group.
[0019]
Examples of the alkyl-substituted pyridine represented by the general formula [I] include 2,4,6-trimethylpyridine, 2,3,6-trimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6- Examples include dimethylpyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3-ethyl-6-methylpyridine, 4-isopropylpyridine, 2-propylpyridine, 2,3,5,6-tetramethylpyridine and the like. it can. Preferred alkyl-substituted pyridines are pyridines that are alkyl-substituted at least in the 2-position and / or 6-position. A particularly preferred compound is 2,4,6-trimethylpyridine.
[0020]
When the catalyst of the present invention is synthesized by reacting the above alkylaluminum compound, phosphorus oxoacid compound, and nitrogen-containing cyclic compound, the ratio of alkylaluminum and phosphorus oxoacid compound is such that the phosphorus oxoacid compound is in the molecule. Depending on the number of moles of OH groups (the sum of the OH groups of the oxo acid compound and the water OH group when the oxo acid compound contains water), the alkylaluminum compound 0.65 to 0 per mole of the OH group .95 moles, preferably in the range of 0.7 to 0.93 moles. When this ratio is out of the above range, the amount of the polymer adhering to the reaction vessel wall increases when used in suspension precipitation polymerization, which is not preferable.
The ratio of the nitrogen-containing cyclic compound is preferably 0.01 to 0.5 mol, more preferably 0.03 to 0.25 mol, relative to 1 mol of the alkylaluminum compound. When the ratio of the nitrogen-containing compound is outside this range, the polymerization activity of the resulting catalyst with respect to the oxirane compound tends to decrease.
[0021]
The reaction sequence of these three raw materials is not particularly limited. First, an alkylaluminum compound and a phosphorus oxo acid compound may be reacted, and then this reaction product may be reacted with a nitrogen-containing cyclic compound. Alternatively, the alkylaluminum compound and the nitrogen-containing cyclic compound may be reacted first, and then the reaction product may be reacted with a phosphorus oxoacid compound. There is no significant difference in the polymerization activity of the resulting catalyst with respect to the oxirane compound. The reaction temperature for each of the above reactions is appropriately selected depending on the alkylaluminum compound or phosphorus oxoacid compound used, but is usually in the range of -20 ° C to 120 ° C. The catalyst synthesis reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or in a solvent-free or inert solvent. The inert solvent is not particularly limited. For example, aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether, dipropyl ether, methyl Examples thereof include ethers such as butyl ether and dimethoxyethane, and these are used alone or as a mixed solvent of two or more.
[0022]
The catalyst obtained by the reaction of the above alkylaluminum, phosphorus oxoacid compound, and nitrogen-containing cyclic compound is very suitable for suspension precipitation polymerization of an oxirane compound. Examples of the oxirane compound that can be polymerized include alkylene oxides such as ethylene oxide, propylene oxide, butene oxide, isobutylene oxide, and butadiene monooxide; epichlorohydrin, epibromohydrin, methacrylic chloride oxide, trifluoromethylethylene oxide, dichloroisobutylene oxide, Substituted alkylene oxides such as styrene oxide; alicyclic epoxides such as cyclohexene oxide and vinylcyclohexene oxide; allyl glycidyl ether, phenyl glycidyl ether, chloroethyl glycidyl ether, methyl glycidyl ether, 2-methoxyethyl glycidyl ether, 2- (2 -Methoxyethoxy) ethyl glycidyl ether, cyclohexyl glycidyl ether, Glycidyl ethers Nji glycidyl ether; glycidyl acrylate and glycidyl esters such as glycidyl methacrylate. Among these, it is preferable to perform homopolymerization or copolymerization of two or more kinds of oxirane compounds represented by the following general formula [III] because the polymerization rate is high and the molecular weight of the resulting polymer increases.
[0023]
[Chemical 6]

(In the formula, m is 0 or 1. R ₆ is a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group or a (meth) acryloyl group. The substituent is a halogen, a methoxy group, an ethoxy group or a methoxyethoxy group.)
[0024]
In the polymerization method according to the present invention, in the presence of the above catalyst, the monomer oxirane compound is suspended and polymerized in an organic solvent that is inert to the monomer and does not dissolve the resulting polymer. This is a method for producing a polymer of a compound.
[0025]
The monomer may be soluble or insoluble in an organic solvent, but it is preferable that at least a part of the monomer is soluble. Examples of such solvents include aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether, dipropyl ether, methylbutyl ether, dimethoxyethane, and the like. Examples include ethers and the like, which are appropriately selected according to the type of oxirane compound used and the polymerization temperature. Preferably, aliphatic hydrocarbons are used.
[0026]
The mixing ratio of the monomer oxirane compound, the organic solvent and the catalyst is usually preferably in the range of 100 to 1000 parts by weight of the organic solvent and 0.01 to 5 parts by weight of the catalyst with respect to 100 parts by weight of the oxirane compound. . The polymerization temperature is not particularly limited, but is usually in the range of −20 ° C. to 150 ° C., and is appropriately selected according to the activity of the catalyst, the organic solvent used, and the type of oxirane compound. The polymerization is usually carried out with stirring.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.
[Example 1]
To a glass flask having a capacity of 300 ml with the inside replaced with nitrogen, 39 ml of triisobutylaluminum was added, and then 81 ml of hexane was added, and the whole was stirred. A solution prepared by dissolving 6.08 g of phosphoric acid (equivalent to 100% by weight of H ₃ PO ₄ ) in 180 ml of diethyl ether is gradually added to a hexane solution of triisobutylaluminum with stirring while adjusting the reaction temperature to about 5 ° C. In addition, both were reacted (the addition ratio of phosphoric acid corresponds to 0.83 mol of triisobutylaluminum with respect to 1 mol of OH group of phosphoric acid). To this reaction solution, 1.5 ml of 2,4,6-trimethylpyridine (pKa = 7.43) was added as a nitrogen-containing cyclic compound with stirring, and stirring was continued at 60 ° C. for 1 hour. A catalyst was thus prepared.
[0028]
Place 18 liters of epichlorohydrin and 9 liters of hexane in a stainless steel reaction vessel with a capacity of 20 liters, the inside of which is purged with nitrogen, add the total amount of the above catalyst, and conduct the polymerization reaction for 6 hours while stirring the whole at 20 ° C. It was. A particulate polymer having a diameter of about 1 mm was deposited in the reaction vessel. The amount of polymer adhering to the reaction vessel wall was 2.8%. In addition, the reaction tank wall adhesion amount of the polymer was calculated by the following formula:
[Formula 1]

[0029]
[Example 2]
A catalyst was prepared in the same procedure as in Example 1 except that 1.5 ml of 2,4-dimethylpyridine (pKa = 6.74) was used as the nitrogen-containing cyclic compound, and the polymerization reaction was performed using this catalyst. went. A particulate polymer having a diameter of about 1 mm was deposited in the reaction vessel. The amount of wall adhesion was 3.6%.
[0031]
[Example 3 ]
Except that the addition amount of phosphoric acid (corresponding to 100% by weight of H ₃ PO ₄ ) was 7.24 g (corresponding to 0.70 mol of triisobutylaluminum with respect to 1 mol of OH group of phosphoric acid), Example 1 and A catalyst was prepared in the same procedure, and a polymerization reaction was performed using the catalyst. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction vessel. The amount of wall adhesion was 4.8%.
[0032]
[Example 4 ]
Except that the addition amount of phosphoric acid (corresponding to 100% by weight of H ₃ PO ₄ ) was 5.47 g (corresponding to 0.93 mol of triisobutylaluminum with respect to 1 mol of OH group of phosphoric acid), Example 1 and A catalyst was prepared in the same procedure, and a polymerization reaction was performed using the catalyst. A particulate polymer having a diameter of about 1.0 mm was deposited in the reaction vessel. The amount of wall adhesion was 6.1%.
[0033]
[Example 5 ]
As an oxo acid compound of phosphorus, 21 g of acidic ethyl phosphate (phosphorus content 21% by weight) which is a partial ethyl ester of phosphoric acid (corresponding to 0.83 mol of triisobutylaluminum with respect to 1 mol of OH group of acidic ethyl phosphate) A catalyst was prepared in the same procedure as in Example 1 except that a polymerization reaction was carried out. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction vessel. The amount of wall adhesion was 5.9%.
[0034]
[Example 6 ]
As an oxo acid compound of phosphorus, phosphoric acid in an aqueous solution form (equivalent to 85% by weight of H ₃ PO ₄ ) is 5.4 g (0.83 mol of triisobutylaluminum with respect to 1 mol of a total of OH groups of phosphoric acid and OH groups of water) Except for the points used, a catalyst was prepared in the same procedure as in Example 1, and a polymerization reaction was performed using this catalyst. A particulate polymer having a diameter of about 1 mm was deposited in the reaction vessel. The amount of wall adhesion was 5.9%.
[0035]
[Example 7 ]
As an alkylaluminum compound, 37 ml of triethylaluminum was used, and 10.7 g of phosphoric acid (corresponding to 100% by weight of H ₃ PO ₄ ) (corresponding to 0.83 mol of triethylaluminum with respect to 1 mol of OH group of phosphoric acid), 2 Except for the addition of 2.7 ml of, 4,6-trimethylpyridine, a catalyst was prepared in the same procedure as in Example 1, and a polymerization reaction was performed using this catalyst. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction vessel. The amount of wall adhesion was 4.8%.
[0036]
[Example 8 ]
A catalyst was prepared in the same procedure as in Example 1, and then the polymerization reaction was carried out in the same procedure as in Example 1, except that 1.5 liter of epichlorohydrin and 0.6 liter of ethylene oxide were used as the oxirane compound. . A particulate copolymer having a diameter of about 1 mm was deposited in the reaction vessel. The amount of wall adhesion was 4.1%.
[0037]
[Example 9 ]
A catalyst was prepared by the same procedure as in Example 1, and then the same procedure as in Example 1 except that 0.8 liter of propylene oxide, 0.9 liter of ethylene oxide and 120 ml of allyl glycidyl ether were used as the oxirane compound. The polymerization reaction was carried out. A particulate terpolymer having a diameter of about 1 mm was deposited in the reaction vessel. The amount of wall adhesion was 4.9%.
[0038]
[Example 10 ]
A catalyst was prepared in the same procedure as in Example 1, and then the polymerization reaction was performed in the same procedure as in Example 1 except that 1.8 liter of styrene oxide was used as the oxirane compound. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction vessel. The amount of wall adhesion was 6.3%.
[0039]
[Comparative Example 1]
Except that the addition amount of phosphoric acid (corresponding to 100% by weight of H ₃ PO ₄ ) was 5.07 g (corresponding to 1.00 mol of triisobutylaluminum with respect to 1 mol of OH group of phosphoric acid), Example 1 and A catalyst was prepared in the same procedure, and a polymerization reaction was performed using the catalyst. A particulate polymer having a diameter of about 1.0 mm was deposited in the reaction vessel. The amount of wall adhesion was 12.4%.
[0040]
[Comparative Example 2]
Except that the addition amount of phosphoric acid (equivalent to 100% by weight of H ₃ PO ₄ ) was 8.45 g (corresponding to 0.60 mol of triisobutylaluminum with respect to 1 mol of OH group of phosphoric acid), Example 1 and A catalyst was prepared in the same procedure, and a polymerization reaction was performed using the catalyst. A particulate polymer having a diameter of about 1.5 mm was deposited in the reaction vessel. The amount of wall adhesion was 16.8%.
[0041]
[Comparative Example 3]
The catalyst was prepared in the same procedure as in Example 1 except that 1.5 ml of 1,8-diazabicyclo [5,4,0] -7-undecene (pKa = 12.5) was used as the nitrogen-containing cyclic compound. It was prepared and a polymerization reaction was performed using this. A large granular polymer having a diameter of about 8 mm was deposited in the reaction vessel. The amount of wall adhesion was 18.5%.
[0042]
[Comparative Example 4]
A catalyst was prepared in the same procedure as in Example 1 except that 1.5 ml of 2-ethylpyridine (pKa = 5.89) was used as a nitrogen-containing cyclic compound, and a polymerization reaction was performed using this catalyst. . A large granular polymer having a diameter of about 15 mm was deposited in the reaction vessel. The amount of wall adhesion was 26.2%.
[0043]
[Evaluation of polymer]
The obtained polymer (including the deposits on the reaction vessel wall) was sufficiently vacuum-dried and weighed to determine the polymer yield. The obtained polymer was vacuum-dried and then dissolved in dimethylformamide, the molecular weight of the polymer was determined by gel permeation chromatography, and the weight average molecular weight was calculated in terms of standard polystyrene. These evaluation results are shown in Table 1.
[0044]
[Table 1]

[0045]
As is apparent from the appearance of the precipitated polymer, when the polymerization of epichlorohydrin is performed using the catalysts obtained in Examples 1 to 7 , a fine particulate homopolymer is obtained and the amount of wall adhesion is small. It has become. Further, as is clear from Table 1, in these examples, both the polymer yield and the molecular weight of the obtained polymer showed high numerical values. In Examples 8 to 10 in which (co) polymerization was carried out using different monomers, a particulate polymer was obtained with a small amount of wall adhesion, and even in these Examples, the polymer yield was obtained. Both molecular weights of the polymers were high.
[0046]
On the other hand, in Comparative Example 1 and Comparative Example 2 in which the value of alkylaluminum with respect to 1 mol of OH groups of the oxo acid compound is out of the range of 0.65 to 0.95 mol, although a particulate polymer is obtained, The amount of adhesion has increased. In Comparative Example 3 using 1,8-diazabicyclo [5,4,0] -7-undecene and Comparative Example 4 using 2-ethylpyridine, the polymer yield and the molecular weight of the polymer are considerably high. It can be seen that the polymer is obtained in large particles and these compounds are not suitable as a catalyst for suspension precipitation polymerization.
[0047]
【The invention's effect】
The oxirane compound polymerization catalyst according to the present invention is configured as described above. By using this catalyst, a high molecular weight polymer can be obtained with high production efficiency, and the amount of polymer attached to the reaction vessel wall. Less is. Therefore, by using the catalyst according to the present invention, high-quality oxirane compounds used in a very wide range of fields such as rubber parts for automobiles, rubber members for electric and electronic devices, polymers for various plastic blends, polymer solid electrolytes, etc. A polymer can be produced efficiently and easily.

Claims (4)

And (A) an alkyl aluminum compound consists of at least the oxo acid compound of phosphorus with one OH group, an alkyl-substituted pyridine represented by (C) the following general formula [I] in the (B) molecules, the (A ) The ratio of the alkylaluminum compound and (B) the phosphorus oxoacid compound having at least one OH group in the molecule, the OH group of the oxoacid compound (if the oxoacid compound contains water, the OH group of the oxoacid compound) ( Total of OH groups in water) is within a range of 0.65 to 0.95 mol of alkylaluminum per 1 mol, and (B) an oxoacid compound of phosphorus is represented by the following general formula [ II ] The oxirane compound is suspended in an organic solvent in which the polymer is insoluble, characterized by being a mixture of polyphosphoric acid equivalent to 90 to 110% by weight of H ₃ PO ₄ or acidic phosphoric acid esters. Catalyst for the polymerization of oxirane compounds for the reaction of depolymerization.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different from each other, and are a hydrogen atom or a lower alkyl group.)

(Where n is an integer from 2 to 10) (C) alkyl-substituted pyridine, polymerization catalyst of the oxirane compound of claim 1 which is 2,4,6-trimethylpyridine. The catalyst for polymerization of an oxirane compound according to claim 1 or 2 , wherein the oxirane compound is a compound represented by the following general formula [III].

(In the formula, m is 0 or 1. R ₆ is a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group, a phenyl group, an aralkyl group, an alkenyl group or a (meth) acryloyl group. The substituent is a halogen, a methoxy group, an ethoxy group or a methoxyethoxy group.) The catalyst according to any one of claims 1 to 3 is used in producing a polymer of an oxirane compound by subjecting the oxirane compound to suspension precipitation polymerization in the presence of a catalyst in an organic solvent in which the polymer is insoluble. The manufacturing method of the oxirane compound polymer characterized by the above-mentioned.