JP4278792B2 - Production method of polyether - Google Patents

Description

【０００７】
｛式中、
M:Sc、Y又はランタノイドから選ばれる希土類元素を示す。
L¹,L²,L³:同一又は異なって、酸素又は窒素結合性の配位子を示す。｝
で表される希土類金属化合物、及び有機金属化合物の存在下、一般式(II)〜(V)で表されるエポキシドの少なくとも１種を含むモノマー成分を重合するポリエーテルの製法、及び新規なポリエーテルを提供する。
【０００８】
【化１２】

【０００９】
｛式中、
R¹：水素原子を示すか、置換基を有していてもよい炭素数1〜50の炭化水素基を示すか、炭素数1〜30のアシル基を示すか、炭素数1〜30のアルキルスルホニル基もしくは炭素数6〜30のアリールスルホニル基を示すか、又は−(AO)n−R³で表される基を示す。ここでR³は、置換基を有していてもよい炭素数1〜30の炭化水素基、炭素数1〜30フルオロアルキル基、炭素数1〜30フルオロアルケニル基もしくは炭素数6〜30のフルオロアリール基を示すか、又はケイ素原子数1〜50のシロキシシリル基を示す。Aは炭素数2〜3のアルキレン基を示し、nは平均値が1〜1000の数を示す。
なお、R¹で示される炭化水素基、アシル基、アルキルスルホニル基、アリールスルホニル基の炭素原子に結合する水素原子の一部又は全部はフッ素原子で置換されていてもよい。
R²：エポキシ環に結合しうる置換基（以下、直接結合性置換基という）を示すか、R¹と同じ意味を示し、３個のR²は同一でも異なっていてもよい。但しR²の全てが同時に水素原子となるものを除く。｝
【００１０】
【化１３】

【００１１】
｛式中、
R⁴：水素原子を示すか、直接結合性置換基を示すか、置換基を有していてもよい炭素数1〜50の炭化水素基を示すか、炭素数1〜30のアシル基を示すか、炭素数1〜30のアルキルスルホニル基もしくは炭素数6〜30のアリールスルホニル基を示すか又は−(AO)n−R³（R³,A及びnは前記と同じ意味を示す）で表される基を示し、炭化水素基、アシル基、アルキルスルホニル基、アリールスルホニル基の炭素原子に結合する水素原子の一部又は全部はフッ素原子で置換されていてもよく、複数個のR⁴は同一でも異なっていてもよい。但し、R⁴のすべてが同時に水素原子であるものを除く。また、R⁴のうち3つが水素原子である場合は、残りの一つは置換基を有さない炭素数1〜50の炭化水素基であるものを除く。｝
【００１２】
【化１４】

【００１３】
（式中、R⁴は前記と同じ意味を示し、複数個のR⁴は同一でも異なっていてもよい。）
【００１４】
【化１５】

【００１５】
（式中、R⁴は前記と同じ意味を示し、複数個のR⁴は同一でも異なっていてもよい。）
【００１６】
【発明の実施の形態】
＜エポキシド＞
一般式(II)〜(V)で表されるエポキシドのR¹及びR⁴における置換基を有していてもよい炭化水素基の具体例として、炭素数1〜50のアルキル基もしくはアルケニル基、又は炭素数6〜50のアリール基が例示され、さらにはそれらが組み合わさってなる炭化水素基も含まれる。炭化水素基の置換基として、ハロゲン原子、ジアゾ基、ヒドロキシル基、ニトリル基、アンモニウム基、ニトロ基、イソシアネート基、アミノ基、メルカプト基、カルボキシル基、カルボキシレート基、アルデヒド基、カルボニル基、エステル基、エーテル基、アミド基、スルフィド基、スルフェニル基、スルホニル基、ホスフィン基、次亜リン酸基、亜リン酸基、リン酸基、ホスホニウム基、シリル基、シロキシ基（以下、「本発明の置換基」という)等が例示される。
【００１７】
アシル基の好ましい例として、総炭素数4〜22のアシル基が例示され、このアシル基における炭化水素基はアルケニル基でもよい。また、アリールスルホニル基の好ましい例として、ベンゼンスルホニル基、トルエンスルホニル基、ニトロベンゼンスルホニル基等が例示される。
【００１８】
R²及びR⁴における直接結合性置換基の具体例として、上記の「本発明の置換基」等が例示される。
【００１９】
R³における置換基を有していてもよい炭化水素基の具体例として、炭素数１〜30のアルキル基もしくはアルケニル基、又は炭素数6〜30のアリール基が例示され、炭化水素基の置換基として、上記の「本発明の置換基」等が例示される。フルオロアルキル又はアルケニル基の好ましい例として、トリフルオロメチル、ペンタフルオロエチル、ノナフルオロブチル、パーフルオロヘキシル、パーフルオロオクチル、パーフルオロドデシル、パーフルオロ−３−メチルブチル、パーフルオロ−５−メチルヘキシル、パーフルオロ−７−メチルオクチル、パーフルオロ−９−メチルデシル、１，１−ジフルオロメチル、１，１，２，２−テトラフルオロエチル、４Ｈ−オクタフルオロブチル、５Ｈ−デカフルオロペンチル、６Ｈ−ドデカフルオロヘキシル、８Ｈ−ヘキサデカフルオロオクチル、１０Ｈ−イコサフルオロデシル、トリフルオロエテニルが挙げられ、フルオロアリール基の好ましい例として、パーフルオロフェニルが挙げられる。
【００２０】
一般式(II)〜(V)で表されるエポキシドは二種以上を共重合できる。また、これらのうち一種以上と、エチレンオキシド、プロピレンオキシド及び／又はエピハロヒドリン等、他のエポキシドとを共重合することができる。さらにこれらのうち一種以上とアニオン重合性モノマーとを共重合することができる。アニオン重合性モノマーとして、スチレン、ビニルナフタレン、1,3-ブタジエン、イソプレン、エチレン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-シクロヘキサジエン、ビニルピリジン、メチル（メタ）アクリレート等の（メタ）アクリル酸エステル類、エピスルフィド、4又は6又は7員環ラクトン類、5又は6員環カーボネート類、ラクタム類、D3（ヘキサメチルシクロトリシロキサン）、D4（オクタメチルシクロテトラシロキサン）等の環状シリコーン類等が例示できるが、好ましくは、スチレン、1,3-ブタジエン、イソプレン、メチルメタクリレート、β-ラクトン、ヘキサメチルシクロトリシロキサンである。
【００２１】
＜希土類金属化合物＞
一般式(I)で表される希土類金属化合物において、Mとして、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Luがあげられるが、重合活性及び経済性の点から、Sc、Y、La、Nd、Sm、Eu、Gd、Dy、Er、Yb、Luが好ましい。
【００２２】
L¹、L²、L³は、酸素又は窒素結合性の配位子であって、例えば、メトキシ基、エトキシ基、n-プロポキシ基、i-プロポキシ基、ブトキシ基、アリロキシ基、メトキシエトキシ基、フェノキシ基、2-メトキシプロポキシ基、トリフルオロエトキシ基、ニトリル基、アルキルアミン類（ジメチルアミン、ジエチルアミン、t-ブチルアミン等）、ジフェニルアミン、ピリジン誘導体（ピリジン、ジ-2-ピリジニルエチレン、2,2'-ビピリジン、フェナントロリン等）、ピリダジン、トリメチルシリルアミン、ジトリメチルシリルアミン、ジメチルピラゾレート、ヒドラジン、ベンズアルデヒドアジン、アゾベンゼン、ポルフィリン類、2,4-ペンタンジオネート基（アセチルアセトネート基）、トリフルオロペンタンジオネート基、ヘキサフルオロペンタンジオネート基、6,6,7,7,8,8,8-ヘプタフルオロ-2,2-ジメチル-3,5-オクタンジオネート基、2,2,6,6-テトラメチル-3,5-ヘプタンジオネート基、チエノイルトリフルオロアセテート基、フロイルトリフルオロアセテート基、ベンゾイルアセトネート基、ベンゾイルトリフルオロアセテート基、アセテート基、トリフルオロアセテート基、メチルアセトアセテート基、エチルアセトアセテート基、メチル（トリメチル）アセチルアセテート基、1,3-ジフェニル-1,3-プロパンジオネート基、メチルスルホネート基、トリフルオロメチルスルホネート基、ジメチルカルバメート基、ジエチルカルバメート基、ニトリト基、ヒドロキサマート基や、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、エチレンジアミンテトラキスメチレンホスホン酸、ヒドロキシエチレンジアミン三酢酸、アゾメテンH、シトラコン酸、イミノジ酢酸、アミノ酸類等が挙げられる。
【００２３】
また、L¹、L²、L³は、全て同一構造式で示される配位子である必要はなく、また、電荷調整のため、他の配位子を有するか塩形成をしていてもよい。
【００２４】
これらの中では、重合活性及び経済性の点から、ｉ-プロポキシ基、2,4-ペンタンジオネート基（アセチルアセトネート基）、トリフルオロペンタンジオネート基、ヘキサフルオロペンタンジオネート基、2,2,6,6-テトラメチル-3,5-ヘプタンジオネート基、アセテート基、トリフルオロアセテート基が好ましい。
【００２５】
希土類金属化合物は、例えば希土類金属ハロゲン化物、酸化物、水酸化物、あるいは硝酸塩と、前記配位子を与える前駆体化合物との反応で簡便に合成できる。これらはあらかじめ合成、精製の上用いても良いし、重合系中で希土類金属化合物と前記配位子を与える前駆体化合物とを混合して用いても良い。
【００２６】
また希土類金属化合物は必要に応じて適当な担体に担持して用いることもでき、例えば、無機酸化物担体、粘土鉱物等の層状珪酸塩、活性炭、金属塩化物、その他無機担体、有機担体の何れを用いても良い。また担持方法は公知の方法を適宜利用できる。
【００２７】
希土類金属化合物の使用量は、該化合物の重合能力並びにモノマーの重合能や使用量、また目的とする重合度や重合系に存在する重合阻害性物質の総量により適宜決定すればよく、例えば、モノマーのモル数に対し、好ましくは0.000001から10当量、より好ましくは0.0001〜5当量、更に好ましくは0.002〜2当量である。0.000001当量以上では高い重合活性が得られ、また10当量以下では低分子量重合体の生成を抑制することができる。
【００２８】
＜有機金属化合物＞
有機金属化合物は、一般式(I)で表される希土類金属化合物のすべて又は一部と反応し、重合活性の極めて高い希土類金属種を発生させる能力があれば何でもよく、(i)トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム等の有機アルミニウム化合物、又はこれらと水の二元系触媒、またこれにアルコール又はキレート化合物を添加した三元系触媒、(ii)アルミニウムトリアルコキシド、(iii)ジアルキルアルミニウムアルコキシド、(iv)ジアルキルアルミニウムヒドリド、(v)アルキルアルミニウムジアルコキシド、(vi)メチルアルミノキサン、(vii)有機アルミニウム硫酸塩、(viii)ジメチル亜鉛、ジエチル亜鉛等の有機亜鉛化合物と水との二元系触媒、又はこれにアルコール又はキレート化合物を添加した三元系触媒、(ix)亜鉛アルコキシド、(x)アルキルリチウム等の有機リチウム化合物、及びこれらと水の混合物、(xi)アルキルマグネシウム等の有機マグネシウム化合物、及びこれらと水の混合物、(xii)その他の反応性を有する有機、無機化合物を用いることができる。その中でも(i)、(vi)、(viii)、(xi)が好ましい。
【００２９】
これらの有機金属化合物は希土類金属化合物とあらかじめ混合、反応させた上用いても良いし、重合系中で混合して用いても良い。なお、あらかじめ混合、反応させた上で用いる際は、適当な温度下に保持、熟成させて用いても良く、この熟成操作によって更に重合活性を高めることができる。
【００３０】
有機金属化合物の使用量は、その反応性、並びに希土類金属化合物の種類や使用量により適宜決定すればよい。有機金属化合物が、アルミニウム、亜鉛、リチウム、マグネシウム等の金属を含有してなる化合物の場合、その金属種の使用モル数は、希土類金属種の使用モル数に対して、好ましくは0.001〜200当量、より好ましくは0.01〜100当量であり、0.1〜50当量であることが特に好ましい。0.001当量以上では高い重合活性が得られ、200当量以下では低分子量重合体の生成を抑制することができる。
【００３１】
＜エポキシドの開環重合＞
本発明を実施するに当たって、重合温度は−78〜220℃、特に−30〜160℃の範囲が好ましい。重合温度域において融解状態にあるエポキシドの重合は無溶媒下で行うことも可能だが、通常は不活性な溶媒中で行うことが望ましい。かかる溶媒としては、ベンゼン、トルエン、キシレン、エチルベンゼン、n-ペンタン、n-ヘキサン、n-ヘプタン、イソオクタン、シクロヘキサン等の炭化水素類、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、塩化メチレン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類や、N,N-ジメチルスルホキシド、またこれらの混合物が挙げられる。これら重合溶媒は、十分に脱水、脱気して用いるのがよい。また、重合温度域において気体状態にあるエポキシドの重合は、エポキシド気流中で行うこともできる。
【００３２】
本発明の重合反応は酸素を排した条件で行うのが望ましい。具体的には窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下、脱気減圧下、脱気溶媒蒸気封入下、又はエポキシド気流下で行うのが望ましい。重合圧力は、常圧、加圧、減圧いずれでも良い。
【００３３】
本発明の重合反応は任意の混合方式で行うことができ、エポキシド、希土類金属化合物並びに有機金属化合物の三者を一度に混合しても良いし、あらかじめこれらのうち一者又は二者を含む系に残りの二者又は一者を加えてもよい。
【００３４】
本発明を実施するに当たって、エポキシドは一般式(II)〜（V）のうち一種以上を用いることができる。また、これらとエチレンオキシド、プロピレンオキシド、エピクロロヒドリン等、他のエポキシドを併用することもできる。二種以上のエポキシドを用いる際は、これらを同時に混合して用いてもよいし、順次重合系に導入することもできる。
【００３５】
さらに本発明を実施するに当たっては、一般式(II)〜（V）のエポキシドのうち一種以上とエポキシド以外のアニオン重合性モノマーの一種以上を併用することができる。これらは同時に混合して用いても良いし、順次重合系に導入しても良い。
【００３６】
＜ポリエーテル＞
本発明の製法により得られるポリエーテルは、例えば、一般式(VI)〜(X)で表される。
【００３７】
【化１６】

【００３８】
｛式中、
R¹、R²：一般式(II)中のR¹、R²と同じ意味を示す。但し、R²のうち少なくとも一つは直接結合性置換基又は炭素数６以上の炭化水素基である。
a：平均値が10以上の数を示し、好ましくは50以上、さらに好ましくは150〜1,000,000である。｝
【００３９】
【化１７】

【００４０】
｛式中、
R⁴：一般式(III)中のR⁴と同じ意味を示す。但し、R⁴のうち少なくとも一つは直接結合性置換基又は炭素数６以上の炭化水素基である。
b：平均値が10以上の数を示し、好ましくは50以上、さらに好ましくは150〜1,000,000である。｝
【００４１】
【化１８】

【００４２】
｛式中、
R⁴：一般式(IV)中のR⁴と同じ意味を示す。但し、R⁴のうち少なくとも一つは直接結合性置換基又は炭素数６以上の炭化水素基である。
d：平均値が10以上の数を示し、好ましくは50以上、さらに好ましくは150〜1,000,000である。｝
【００４３】
【化１９】

【００４４】
｛式中、
R⁴：一般式(V)中のR⁴と同じ意味を示す。但し、R⁴のうち少なくとも一つは直接結合性置換基又は炭素数６以上の炭化水素基である。
e：平均値が10以上の数を示し、好ましくは50以上、さらに好ましくは150〜1,000,000である。｝
【００４５】
【化２０】

【００４６】
｛式中、
Ｘ,Ｙ：一般式(VI)〜(IX)で表される構造単位、及び他のエポキシド又は他のアニオン重合性構造単位のうちの任意の二つを示す。但しＸ,Ｙのうち少なくとも一方は一般式(VI)〜(IX)で表される構造単位を有するものとし、またＸとＹが同一である場合を除く。
f、g：平均値がそれぞれ10以上の数を示し、好ましくは50以上、さらに好ましくは150〜1,000,000である。｝
ここで他のエポキシドの具体例として、エチレンオキシド、プロピレンオキシド、エピハロヒドリン等が挙げられ、アニオン重合性構造単位の具体例として、スチレン、メチルメタクリレート、メチルアクリレート、エチレン、イソプレン、ブタジエン、D3、D4、ラクトン等から誘導される構造単位が挙げられる。
【００４７】
一般式(X)で表される共重合体は、二元系以上である。一般式(X)において、ＸとＹはランダム型になっていてもよいしブロック型になっていてもよい。
【００４８】
【実施例】
＜触媒調製及び重合＞
触媒調製及び重合は、乾燥窒素雰囲気下で行った。各種の溶媒は、乾燥後、蒸留、脱気したものを使用した。希土類金属化合物及びその他の無機化合物は、市販高純度品をそのまま使用した。メチルアルモキサン（以下ＭＡＯという）溶液（ここで用いたのはトルエン溶液で、アルミニウム濃度は10.2重量%）及びジエチル亜鉛は市販品をそのまま使用した。
【００４９】
触媒調製例１
サマリウムトリイソプロポキシド0.9296gを秤量し、トルエン23.83mlを加え攪拌した。攪拌下に室温でＭＡＯ溶液5.06ml(6当量)を滴下し、触媒Ａ(Sm／Al（モル比）=1／6)を調整した。
【００５０】
触媒調製例２
サマリウムトリス（テトラメチルヘプタンジオネート）0.5192gを秤量し、トルエン7.20mlを加え、加熱攪拌した。室温まで放冷後、攪拌下にＭＡＯ溶液0.22ml(1当量)を滴下し、触媒Ｂ(Sm／Al（モル比）=1／1)を調整した。
【００５１】
実施例１
ポリ(2-メチルグリシジル-4-ニトロベンゾエート）：一般式(VI)において、R¹＝4-ニトロベンゾイル、R²＝メチル、水素原子×２
2-メチルグリシジル-4-ニトロベンゾエート4gを窒素置換した容器に取り、トルエン5.7mlを加え溶解させた。これに触媒Ａ1.00mlを添加した後、容器を封栓し、攪拌しながら130℃で重合した。重合終了後、反応液を少量の希塩酸を加えたアセトンに添加した。析出した白色固体を80℃で24時間減圧乾燥し、ポリ（2-メチルグリシジル-4-ニトロベンゾエート）を得た。収率80%。
【００５２】
GPC分析（130℃、o-ジクロロベンゼン、ポリスチレン換算分子量）によれば、数平均分子量(Mn)=5万、重量平均分子量(Mw)=105万であった。測定は、ウォータース社製150C型を使用し、カラムは昭和電工社製ShodexHT-806M×1本、ShodexHT-803×2本を使用した。以下の実施例、比較例において130℃で測定したときはこの条件で行った。
【００５３】
実施例２
ポリ(2-メチルグリシジル-4-ニトロベンゾエート）：一般式(VI)において、R¹＝4-ニトロベンゾイル、R²＝メチル、水素原子×２
触媒Ａの代わりに触媒Ｂを用いること以外は実施例1記載の方法と同様にしてポリエーテルを得た。収率95%。
GPC分析(130℃)によれば、Mn=12万、Mw=150万であった。
【００５４】
実施例３
ポリ（2,3-エポキシブタン）：一般式（VII）において、R⁴=メチル×２、水素原子×２
2,3-エポキシブタン4gを窒素置換した容器に取り、トルエン5.7mlを加え溶解させた。これに触媒Ｂ1.50mlを添加した後、容器を封栓し、攪拌しながら130℃で重合した。重合終了後、容器を開封し、反応液を少量の希塩酸を加えたアセトンに添加した。析出した白色固体を80℃で24時間減圧乾燥し、ポリ（2,3-エポキシブタン）を得た。収率80%。
GPC分析(130℃)によれば、Mn=1.2万、Mw=15万であった。
【００５５】
実施例４
ポリ（エポキシコハク酸ジエチル）：一般式(VII)において、R⁴＝COOC₂H₄×２，水素原子×２
エポキシコハク酸ジエチル4gを実施例３と同様にして重合し、ポリ（エポキシコハク酸ジエチル）を得た。収率88%。
GPC分析(130℃)によれば、Mn=1.2万、Mw=15万であった。
【００５６】
実施例５
ポリ（2-メチルグリシジル-4-ニトロベンゾエート／メチルグリシジルエーテル）：一般式(X)において、
【００５７】
【化２１】

【００５８】
2-メチルグリシジル-4-ニトロベンゾエート3g及びメチルグリシジルエーテル2gを窒素置換した容器に取り、トルエン5.7mlを加え溶解させた。これに触媒Ｂ 1.50mlを添加した後、容器を封栓し、攪拌しながら130℃で重合した。重合終了後、容器を開封し、反応液を少量の希塩酸を加えたアセトンに添加した。析出した白色固体を80℃で24時間減圧乾燥し、共重合体を得た。収率92%。
GPC分析(130℃)によれば、Mn=1.2万、Mw=15万であった。
NMR分析によれば、共重合体の組成は、2-メチルグリシジル-4-ニトロベンゾエート：メチルグリシジルエーテル＝40：60であった。
【００５９】
実施例６
ポリ（2-メチルグリシジル-4-ニトロベンゾエート／2,3-エポキシブタン）：一般式(X)において、
【００６０】
【化２２】

【００６１】
2-メチルグリシジル-4-ニトロベンゾエート3g及び2,3-エポキシブタン2gを実施例５と同様にして共重合し、共重合体を得た。
GPC分析によれば、Mn=２万、Mw=20万であった。
NMR分析によれば、共重合体の組成は、2-メチルグリシジル-4-ニトロベンゾエート：2,3-エポキシブタン＝30：70であった。
【００６２】
実施例７
ポリ（ビスクロロメチルオキセタン）：一般式(VIII)において、R⁴＝水素原子×４、クロロメチル×２
ビスクロロメチルオキセタン4gを窒素置換した容器に取り、トルエン5.7mlを加え溶解させた。これに触媒B 1.50mlを添加した後、容器を封栓し、攪拌しながら130℃で重合した。重合終了後、容器を開封し、反応液を少量の希塩酸を加えたアセトンに添加した。析出した白色固体を80℃で24時間減圧乾燥し、ポリ（ビスクロロメチルオキセタン）を得た。収率70%。
GPC分析(130℃)によれば、Mn=8千、Mw=2万であった。
【００６３】
実施例８
ポリ（2,5-ジメチルテトラヒドロフラン）：一般式(IX)においてR⁴＝メチル×２、水素原子×６
2,5-ジメチルテトラヒドロフラン4gを実施例７と同様にして重合し、ポリ（2,5-ジメチルテトラヒドロフラン）2.2gを得た。
GPC分析(130℃)によれば、Mn=3千、Mw=1.2万であった。
【００６４】
比較例１
触媒Ａの代わりにトリエチルアルミニウム／水／アセチルアセトンをモル比１／0.5／１で混合して得た触媒の0.1Mトルエン溶液を用いること以外は実施例１記載の方法により2-メチルグリシジル-4-ニトロベンゾエートを重合した。収率3%。
GPC分析(130℃)によれば、本重合体はMn=5000、Mw＝２万であった。
【００６５】
比較例２
触媒Ａの代わりに、ジエチル亜鉛／1-メトキシ-2-プロパノールをモル比1/0.5で混合して得た触媒の0.1Mトルエン溶液を用いること以外は、実施例１記載の方法により2-メチルグリシジル-4-ニトロベンゾエートを重合した。収率35%。
GPC分析(130℃)によれば、本重合体はMn=1.5万、Mw＝6万であった。
【００６６】
比較例３
触媒Ａの代わりに、水酸化セシウム0.75gを用いること以外は、実施例１記載の方法により2-メチルグリシジル-4-ニトロベンゾエートを重合した。再沈殿操作の後、固形物はまったく得られなかった。収率０%
【００６７】
比較例４
触媒Ｂの代わりにトリエチルアルミニウム／水／アセチルアセトンをモル比１／0.5／１で混合して得た触媒の0.1Mトルエン溶液を用いること以外は実施例４記載の方法によりエポキシコハク酸ジエチルを重合した。再沈殿操作の後、固形物はまったく得られなかった。収率０%
【００６８】
比較例５
触媒Ｂの代わりにトリエチルアルミニウム／水／アセチルアセトンをモル比１／0.5／１で混合して得た触媒の0.1Mトルエン溶液を用いること以外は実施例５記載の方法により2-メチルグリシジル-4-ニトロベンゾエートとメチルグリシジルエーテルを共重合した。 収率12%。
GPC分析(130℃)によれば、Mn=1.2万、Mw=15万であった。
NMR分析によれば、共重合体の組成は、2-メチルグリシジル-4-ニトロベンゾエート：メチルグリシジルエーテル＝0：100であり、共重合体は得られなかった。
【００６９】
比較例６
触媒Ｂの代わりにトリエチルアルミニウム／水／アセチルアセトンをモル比１／0.5／１で混合して得た触媒の0.1Mトルエン溶液を用いること以外は実施例７記載の方法によりビスクロロメチルオキセタンを重合した。収率５%。
GPC分析(130℃)によれば、Mn=５千、Mw=1.5万であった。
【００７０】
比較例７
触媒Ｂの代わりにトリエチルアルミニウム／水／アセチルアセトンをモル比１／0.5／１で混合して得た触媒の0.1Mトルエン溶液を用いること以外は実施例８記載の方法により2,5-ジメチルテトラヒドロフランを重合した。再沈殿操作の後、固形物はまったく得られなかった。収率０%
【００７１】
【発明の効果】
本発明によれば、化粧品分野及び化学品分野において有用な高重合度ポリエーテルを容易に収率よく提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a high-polymerization polyether useful in the cosmetics and chemical fields and a novel polyether.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, in the case of ring-opening polymerization of a substituted epoxide, it is known that the molecular weight of a product is generally greatly reduced by chain transfer derived from the extraction of atoms from a substituent. Exceptionally, propylene oxide and epihalohydrin are not significantly deteriorated in polymerizability and can be obtained with a molecular weight of about 1 million depending on the choice of catalyst system, but other substituted epoxides provide high-polymerization degree polyethers with good yields. I couldn't.
[0003]
In recent years, examples using a composition containing a rare earth metal compound as a polymerization catalyst for ethylene oxide, propylene oxide or epichlorohydrin, such as (1) Inorg. Chim. Acta, Vol. 155, 263 (1989), (2) ▼ Polymer J., Vol. 22, 326 (1990), ▲ 3 ▼ Macromol. Chem. Phys., Vol. 196, 2417 (1995). All of these are obtained by polymerizing ethylene oxide, propylene oxide, and epichlorohydrin, and have a molecular weight of about one million. However, this polymerization catalyst is comparable to conventional coordination anionic catalysts, and even if they are used, a high polymerization degree polyether can be obtained by polymerizing epoxides other than propylene oxide and epichlorohydrin. In view of the above, it was not expected that a rare earth metal compound, which had only shown performance equivalent to that of conventional catalysts, would be a useful catalyst for obtaining a high polymerization degree polyether from a substituted epoxide.
[0004]
An object of the present invention is to provide a method for easily obtaining a polyether having a high degree of polymerization by easily polymerizing a substituted epoxide other than propylene oxide and epihalohydrin, which has been extremely difficult or impossible to achieve. There is to do.
[0005]
[Means for Solving the Problems]
The present invention relates to general formula (I)
[0006]
Embedded image

[0007]
{Where,
M: A rare earth element selected from Sc, Y, or a lanthanoid.
L ¹ , L ² , L ^{3 are the} same or different and represent oxygen or nitrogen-bonded ligands. }
A process for producing a polyether that polymerizes a monomer component containing at least one epoxide represented by general formulas (II) to (V) in the presence of a rare earth metal compound represented by formula (II) and an organometallic compound, Provide ether.
[0008]
Embedded image

[0009]
{Where,
R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 50 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an alkyl having 1 to 30 carbon atoms sulfonyl group or or an aryl sulfonyl group having 6 to 30 carbon atoms, or - a group represented by (AO) n-R ^3. R ³ is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a fluoroalkenyl group having 1 to 30 carbon atoms, or a fluoro group having 6 to 30 carbon atoms. It represents an aryl group or a siloxysilyl group having 1 to 50 silicon atoms. A represents an alkylene group having 2 to 3 carbon atoms, and n represents a number having an average value of 1 to 1000.
A part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group, acyl group, alkylsulfonyl group or arylsulfonyl group represented by R ¹ may be substituted with a fluorine atom.
R ^{2 represents a} substituent that can be bonded to the epoxy ring (hereinafter referred to as a direct bonding substituent), or has the same meaning as R ^1, and three R ² may be the same or different. However, the case where all of R ² are simultaneously hydrogen atoms is excluded. }
[0010]
Embedded image

[0011]
{Where,
R ⁴ : represents a hydrogen atom, represents a direct bonding substituent, represents an optionally substituted hydrocarbon group having 1 to 50 carbon atoms, or represents an acyl group having 1 to 30 carbon atoms Table in ^{(AO) n-R 3 (} R 3, a and n are as defined above) - or, or an alkyl sulfonyl group or arylsulfonyl group having 6 to 30 carbon atoms having 1 to 30 carbon atoms A part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group, acyl group, alkylsulfonyl group, arylsulfonyl group may be substituted with a fluorine atom, and a plurality of R ⁴ are It may be the same or different. However, the case where all of R ⁴ are hydrogen atoms at the same time is excluded. In addition, when three of R ⁴ are hydrogen atoms, the other one is a hydrocarbon group having 1 to 50 carbon atoms having no substituent. }
[0012]
Embedded image

[0013]
(Wherein R ⁴ represents the same meaning as described above, and a plurality of R ⁴ may be the same or different.)
[0014]
Embedded image

[0015]
(Wherein R ⁴ represents the same meaning as described above, and a plurality of R ⁴ may be the same or different.)
[0016]
DETAILED DESCRIPTION OF THE INVENTION
<Epoxide>
Specific examples of the hydrocarbon group which may have a substituent in R ¹ and R ⁴ of the epoxide represented by the general formulas (II) to (V) include an alkyl group or alkenyl group having 1 to 50 carbon atoms, Or a C6-C50 aryl group is illustrated, Furthermore, the hydrocarbon group formed by combining them is also contained. As substituents for hydrocarbon groups, halogen atoms, diazo groups, hydroxyl groups, nitrile groups, ammonium groups, nitro groups, isocyanate groups, amino groups, mercapto groups, carboxyl groups, carboxylate groups, aldehyde groups, carbonyl groups, ester groups , Ether group, amide group, sulfide group, sulfenyl group, sulfonyl group, phosphine group, hypophosphite group, phosphorous acid group, phosphoric acid group, phosphonium group, silyl group, siloxy group (hereinafter referred to as “the present invention”). And the like ").
[0017]
Preferred examples of the acyl group include acyl groups having 4 to 22 carbon atoms, and the hydrocarbon group in the acyl group may be an alkenyl group. Further, preferred examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, a nitrobenzenesulfonyl group, and the like.
[0018]
Specific examples of the direct bonding substituent in R ² and R ⁴ include the above-mentioned “substituent of the present invention” and the like.
[0019]
Specific examples of the hydrocarbon group which may have a substituent for R ³ include an alkyl group or an alkenyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Examples of the group include the above-mentioned “substituents of the present invention”. Preferred examples of the fluoroalkyl or alkenyl group include trifluoromethyl, pentafluoroethyl, nonafluorobutyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoro-3-methylbutyl, perfluoro-5-methylhexyl, perfluorohexyl Fluoro-7-methyloctyl, perfluoro-9-methyldecyl, 1,1-difluoromethyl, 1,1,2,2-tetrafluoroethyl, 4H-octafluorobutyl, 5H-decafluoropentyl, 6H-dodecafluorohexyl , 8H-hexadecafluorooctyl, 10H-icosafluorodecyl and trifluoroethenyl, and a preferred example of the fluoroaryl group is perfluorophenyl.
[0020]
Two or more epoxides represented by the general formulas (II) to (V) can be copolymerized. One or more of these can be copolymerized with other epoxides such as ethylene oxide, propylene oxide and / or epihalohydrin. Furthermore, one or more of these and an anion polymerizable monomer can be copolymerized. Anionic polymerizable monomers include styrene, vinyl naphthalene, 1,3-butadiene, isoprene, ethylene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-cyclohexadiene, vinyl pyridine, methyl (Meth) acrylates such as (meth) acrylates, episulfides, 4-, 6- or 7-membered ring lactones, 5- or 6-membered ring carbonates, lactams, D3 (hexamethylcyclotrisiloxane), D4 (octamethyl) Cyclic silicones such as cyclotetrasiloxane can be exemplified, and styrene, 1,3-butadiene, isoprene, methyl methacrylate, β-lactone, and hexamethylcyclotrisiloxane are preferable.
[0021]
<Rare earth metal compound>
In the rare earth metal compound represented by the general formula (I), as M, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu Sc, Y, La, Nd, Sm, Eu, Gd, Dy, Er, Yb, and Lu are preferable from the viewpoint of polymerization activity and economy.
[0022]
L ¹ , L ² and L ³ are oxygen or nitrogen-bonded ligands, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, butoxy group, allyloxy group, methoxyethoxy group , Phenoxy group, 2-methoxypropoxy group, trifluoroethoxy group, nitrile group, alkylamines (dimethylamine, diethylamine, t-butylamine, etc.), diphenylamine, pyridine derivatives (pyridine, di-2-pyridinylethylene, 2 , 2'-bipyridine, phenanthroline, etc.), pyridazine, trimethylsilylamine, ditrimethylsilylamine, dimethylpyrazolate, hydrazine, benzaldehyde azine, azobenzene, porphyrins, 2,4-pentanedionate group (acetylacetonate group), trifluoropentane Dionate group, hexafluoropentane Onate group, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionate group, 2,2,6,6-tetramethyl-3,5- Heptanedionate group, thienoyl trifluoroacetate group, furoyl trifluoroacetate group, benzoyl acetonate group, benzoyl trifluoroacetate group, acetate group, trifluoroacetate group, methyl acetoacetate group, ethyl acetoacetate group, methyl (trimethyl ) Acetyl acetate group, 1,3-diphenyl-1,3-propanedionate group, methyl sulfonate group, trifluoromethyl sulfonate group, dimethyl carbamate group, diethyl carbamate group, nitrito group, hydroxamate group, ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, ethylenediaminetetrakismethylenephosphonic acid, hydroxye Examples include tylenediamine triacetic acid, azomethene H, citraconic acid, iminodiacetic acid, and amino acids.
[0023]
In addition, L ¹ , L ² , and L ³ need not all be ligands represented by the same structural formula, and may have other ligands or form a salt for charge adjustment. Good.
[0024]
Among these, from the viewpoint of polymerization activity and economy, i-propoxy group, 2,4-pentanedionate group (acetylacetonate group), trifluoropentanedionate group, hexafluoropentanedionate group, 2, 2,6,6-tetramethyl-3,5-heptanedionate group, acetate group and trifluoroacetate group are preferred.
[0025]
The rare earth metal compound can be easily synthesized by, for example, reacting a rare earth metal halide, oxide, hydroxide, or nitrate with a precursor compound that gives the ligand. These may be used in advance after synthesis and purification, or may be used by mixing a rare earth metal compound and a precursor compound giving the ligand in a polymerization system.
[0026]
Further, the rare earth metal compound can be used by being supported on a suitable carrier as required. For example, any of inorganic oxide carrier, layered silicate such as clay mineral, activated carbon, metal chloride, other inorganic carrier, organic carrier May be used. Moreover, a well-known method can be utilized suitably for the carrying | support method.
[0027]
The amount of the rare earth metal compound used may be appropriately determined depending on the polymerization ability of the compound, the polymerization ability and use amount of the monomer, the degree of polymerization desired, and the total amount of the polymerization inhibitory substance present in the polymerization system. Is preferably 0.000001 to 10 equivalents, more preferably 0.0001 to 5 equivalents, and still more preferably 0.002 to 2 equivalents. When it is 0.000001 equivalent or more, high polymerization activity can be obtained, and when it is 10 equivalent or less, formation of a low molecular weight polymer can be suppressed.
[0028]
<Organic metal compound>
The organometallic compound may be anything as long as it has the ability to react with all or a part of the rare earth metal compound represented by the general formula (I) to generate a rare earth metal species having extremely high polymerization activity, and (i) trimethylaluminum, Organoaluminum compounds such as triethylaluminum and triisobutylaluminum, or a binary catalyst of these and water, and a ternary catalyst obtained by adding an alcohol or a chelate compound thereto, (ii) aluminum trialkoxide, (iii) dialkylaluminum alkoxide (Iv) dialkylaluminum hydride, (v) alkylaluminum dialkoxide, (vi) methylaluminoxane, (vii) organoaluminum sulfate, (viii) a binary system of an organic zinc compound such as dimethylzinc, diethylzinc and water A catalyst, or a ternary catalyst obtained by adding an alcohol or a chelate compound thereto, (ix) (B) lead alkoxide, organolithium compounds such as (x) alkyl lithium, and mixtures thereof with water, (xi) organomagnesium compounds such as alkyl magnesium, and mixtures thereof with water, (xii) other reactive organics, Inorganic compounds can be used. Of these, (i), (vi), (viii), and (xi) are preferable.
[0029]
These organometallic compounds may be used after being mixed and reacted with a rare earth metal compound in advance, or may be used by mixing in a polymerization system. When used after being mixed and reacted in advance, it may be used after being kept and aged at an appropriate temperature, and the polymerization activity can be further enhanced by this aging operation.
[0030]
What is necessary is just to determine the usage-amount of an organometallic compound suitably with the reactivity and the kind and usage-amount of a rare earth metal compound. When the organometallic compound is a compound containing a metal such as aluminum, zinc, lithium, magnesium, etc., the number of moles of the metal species used is preferably 0.001 to 200 equivalents relative to the number of moles of the rare earth metal species used. More preferably, it is 0.01-100 equivalent, and it is especially preferable that it is 0.1-50 equivalent. When it is 0.001 equivalent or more, high polymerization activity can be obtained, and when it is 200 equivalent or less, formation of a low molecular weight polymer can be suppressed.
[0031]
<Ring-opening polymerization of epoxide>
In practicing the present invention, the polymerization temperature is preferably −78 to 220 ° C., particularly preferably −30 to 160 ° C. The polymerization of the epoxide in the molten state in the polymerization temperature range can be carried out in the absence of a solvent, but it is usually preferably carried out in an inert solvent. Such solvents include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, n-pentane, n-hexane, n-heptane, isooctane and cyclohexane, ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane. , Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, N, N-dimethyl sulfoxide, and mixtures thereof. These polymerization solvents are preferably used after sufficiently dehydrated and degassed. The polymerization of the epoxide that is in a gaseous state in the polymerization temperature range can also be performed in an epoxide stream.
[0032]
The polymerization reaction of the present invention is preferably carried out under conditions where oxygen is eliminated. Specifically, it is desirable to carry out under an inert gas atmosphere such as nitrogen, helium, argon, etc., under a degassing decompression, under a degassing solvent vapor filling, or under an epoxide stream. The polymerization pressure may be normal pressure, increased pressure, or reduced pressure.
[0033]
The polymerization reaction of the present invention can be carried out by any mixing method, and the epoxide, rare earth metal compound and organometallic compound may be mixed at once, or a system including one or two of these in advance. You may add the remaining two or one.
[0034]
In practicing the present invention, one or more of the general formulas (II) to (V) can be used as the epoxide. Moreover, these and other epoxides, such as ethylene oxide, propylene oxide, epichlorohydrin, can also be used together. When two or more kinds of epoxides are used, they may be mixed at the same time or sequentially introduced into the polymerization system.
[0035]
In carrying out the present invention, one or more epoxides of the general formulas (II) to (V) and one or more anionic polymerizable monomers other than the epoxide can be used in combination. These may be mixed and used at the same time, or may be sequentially introduced into the polymerization system.
[0036]
<Polyether>
The polyether obtained by the production method of the present invention is represented by, for example, general formulas (VI) to (X).
[0037]
Embedded image

[0038]
{Where,
R ^1, R ^2: the same meanings as R ^1, R ² in the general formula (II). However, at least one of R ² is a direct bond substituent or a hydrocarbon group having 6 or more carbon atoms.
a: The average value represents a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. }
[0039]
Embedded image

[0040]
{Where,
R ⁴ has the same meaning as R ⁴ in general formula (III). However, at least one of R ⁴ is a direct bond substituent or a hydrocarbon group having 6 or more carbon atoms.
b: The average value represents a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. }
[0041]
Embedded image

[0042]
{Where,
R ⁴ : Shows the same meaning as R ⁴ in general formula (IV). However, at least one of R ⁴ is a direct bond substituent or a hydrocarbon group having 6 or more carbon atoms.
d: The average value represents a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. }
[0043]
Embedded image

[0044]
{Where,
R ⁴ : Shows the same meaning as R ⁴ in general formula (V). However, at least one of R ⁴ is a direct bond substituent or a hydrocarbon group having 6 or more carbon atoms.
e: An average value represents a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. }
[0045]
Embedded image

[0046]
{Where,
X, Y: Arbitrary two of the structural units represented by the general formulas (VI) to (IX) and other epoxides or other anionic polymerizable structural units. However, at least one of X and Y is assumed to have a structural unit represented by general formulas (VI) to (IX), and the case where X and Y are the same is excluded.
f, g: each represents an average value of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. }
Here, specific examples of other epoxides include ethylene oxide, propylene oxide, epihalohydrin, etc. Specific examples of anionic polymerizable structural units include styrene, methyl methacrylate, methyl acrylate, ethylene, isoprene, butadiene, D3, D4, and lactone. And the like derived from structural units.
[0047]
The copolymer represented by the general formula (X) is a binary system or more. In the general formula (X), X and Y may be a random type or a block type.
[0048]
【Example】
<Catalyst preparation and polymerization>
Catalyst preparation and polymerization were performed under a dry nitrogen atmosphere. Various solvents used were dried, distilled and degassed. Commercially available high purity products were used as they were for the rare earth metal compounds and other inorganic compounds. A commercially available product of methylalumoxane (hereinafter referred to as MAO) solution (here used was a toluene solution and the aluminum concentration was 10.2% by weight) and diethylzinc were used as they were.
[0049]
Catalyst preparation example 1
0.9296 g of samarium triisopropoxide was weighed and 23.83 ml of toluene was added and stirred. Under stirring, MAO solution (5.06 ml, 6 equivalents) was added dropwise at room temperature to prepare catalyst A (Sm / Al (molar ratio) = 1/6).
[0050]
Catalyst preparation example 2
0.5192 g of samarium tris (tetramethylheptanedionate) was weighed, 7.20 ml of toluene was added, and the mixture was heated and stirred. After cooling to room temperature, 0.22 ml (1 equivalent) of MAO solution was added dropwise with stirring to prepare catalyst B (Sm / Al (molar ratio) = 1/1).
[0051]
Example 1
Poly (2-methylglycidyl-4-nitrobenzoate): In the general formula (VI), R ¹ = 4-nitrobenzoyl, R ² = methyl, hydrogen atom × 2
4 g of 2-methylglycidyl-4-nitrobenzoate was placed in a container purged with nitrogen, and 5.7 ml of toluene was added and dissolved. After adding 1.00 ml of catalyst A thereto, the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the reaction solution was added to acetone with a small amount of diluted hydrochloric acid added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain poly (2-methylglycidyl-4-nitrobenzoate). Yield 80%.
[0052]
According to GPC analysis (130 ° C., molecular weight in terms of o-dichlorobenzene and polystyrene), the number average molecular weight (Mn) = 50,000 and the weight average molecular weight (Mw) = 1,050,000. For the measurement, a 150C model manufactured by Waters was used, and ShodexHT-806M × 1 and ShodexHT-803 × 2 manufactured by Showa Denko Co., Ltd. were used as columns. When measured at 130 ° C. in the following Examples and Comparative Examples, the measurement was performed under these conditions.
[0053]
Example 2
Poly (2-methylglycidyl-4-nitrobenzoate): In the general formula (VI), R ¹ = 4-nitrobenzoyl, R ² = methyl, hydrogen atom × 2
A polyether was obtained in the same manner as in Example 1 except that catalyst B was used instead of catalyst A. Yield 95%.
According to the GPC analysis (130 ° C.), Mn = 120,000 and Mw = 1,500,000.
[0054]
Example 3
Poly (2,3-epoxybutane): In the general formula (VII), R ⁴ = methyl × 2, hydrogen atom × 2
2,4-epoxybutane 4 g was placed in a nitrogen-substituted container, and 5.7 ml of toluene was added and dissolved. After adding 1.50 ml of catalyst B thereto, the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the container was opened, and the reaction solution was added to acetone with a small amount of diluted hydrochloric acid added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain poly (2,3-epoxybutane). Yield 80%.
According to the GPC analysis (130 ° C.), Mn = 12,000 and Mw = 150,000.
[0055]
Example 4
Poly (diethyl epoxy succinate): In general formula (VII), R ⁴ = COOC ₂ H ₄ × 2, hydrogen atoms × 2
4 g of diethyl epoxy succinate was polymerized in the same manner as in Example 3 to obtain poly (diethyl epoxy succinate). Yield 88%.
According to the GPC analysis (130 ° C.), Mn = 12,000 and Mw = 150,000.
[0056]
Example 5
Poly (2-methylglycidyl-4-nitrobenzoate / methylglycidyl ether): In general formula (X),
[0057]
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[0058]
2 g of 2-methylglycidyl-4-nitrobenzoate and 2 g of methyl glycidyl ether were placed in a container purged with nitrogen, and 5.7 ml of toluene was added and dissolved. After adding 1.50 ml of catalyst B thereto, the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the container was opened, and the reaction solution was added to acetone with a small amount of diluted hydrochloric acid added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain a copolymer. Yield 92%.
According to the GPC analysis (130 ° C.), Mn = 12,000 and Mw = 150,000.
According to NMR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: methylglycidyl ether = 40: 60.
[0059]
Example 6
Poly (2-methylglycidyl-4-nitrobenzoate / 2,3-epoxybutane): In the general formula (X),
[0060]
Embedded image

[0061]
2 g of 2-methylglycidyl-4-nitrobenzoate and 2 g of 2,3-epoxybutane were copolymerized in the same manner as in Example 5 to obtain a copolymer.
According to the GPC analysis, Mn = 20,000 and Mw = 200,000.
According to NMR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: 2,3-epoxybutane = 30: 70.
[0062]
Example 7
Poly (bischloromethyloxetane): In the general formula (VIII), R ⁴ = hydrogen atom × 4, chloromethyl × 2
Bischloromethyloxetane (4 g) was placed in a nitrogen-substituted container, and toluene (5.7 ml) was added and dissolved. After adding 1.50 ml of catalyst B thereto, the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the container was opened, and the reaction solution was added to acetone with a small amount of diluted hydrochloric acid added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain poly (bischloromethyloxetane). Yield 70%.
According to GPC analysis (130 ° C.), Mn = 8,000 and Mw = 20,000.
[0063]
Example 8
Poly (2,5-dimethyltetrahydrofuran): In general formula (IX), R ⁴ = methyl × 2, hydrogen atom × 6
2,5-dimethyltetrahydrofuran (4 g) was polymerized in the same manner as in Example 7 to obtain poly (2,5-dimethyltetrahydrofuran) (2.2 g).
According to the GPC analysis (130 ° C.), Mn = 3,000 and Mw = 12,000.
[0064]
Comparative Example 1
Instead of the catalyst A, 2-methylglycidyl-4-l was prepared by the method described in Example 1 except that a 0.1 M toluene solution of the catalyst obtained by mixing triethylaluminum / water / acetylacetone at a molar ratio of 1 / 0.5 / 1 was used. Nitrobenzoate was polymerized. Yield 3%.
According to GPC analysis (130 ° C.), the polymer had Mn = 5000 and Mw = 20,000.
[0065]
Comparative Example 2
Instead of catalyst A, 2-methyl-methyl was prepared by the method described in Example 1, except that a 0.1 M toluene solution of the catalyst obtained by mixing diethylzinc / 1-methoxy-2-propanol at a molar ratio of 1 / 0.5 was used. Glycidyl-4-nitrobenzoate was polymerized. Yield 35%.
According to GPC analysis (130 ° C.), the polymer had Mn = 15,000 and Mw = 60,000.
[0066]
Comparative Example 3
Instead of catalyst A, 2-methylglycidyl-4-nitrobenzoate was polymerized by the method described in Example 1 except that 0.75 g of cesium hydroxide was used. No solid matter was obtained after the reprecipitation operation. Yield 0%
[0067]
Comparative Example 4
Diethyl epoxy succinate was polymerized by the method described in Example 4 except that a 0.1M toluene solution of a catalyst obtained by mixing triethylaluminum / water / acetylacetone at a molar ratio of 1 / 0.5 / 1 was used instead of catalyst B. . No solid matter was obtained after the reprecipitation operation. Yield 0%
[0068]
Comparative Example 5
Instead of the catalyst B, 2-methylglycidyl-4-methylate according to the method described in Example 5 except that a 0.1M toluene solution of a catalyst obtained by mixing triethylaluminum / water / acetylacetone at a molar ratio of 1 / 0.5 / 1 was used. Nitrobenzoate and methyl glycidyl ether were copolymerized. Yield 12%.
According to the GPC analysis (130 ° C.), Mn = 12,000 and Mw = 150,000.
According to NMR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: methylglycidyl ether = 0: 100, and no copolymer was obtained.
[0069]
Comparative Example 6
Bischloromethyloxetane was polymerized by the method described in Example 7 except that a 0.1 M toluene solution of the catalyst obtained by mixing triethylaluminum / water / acetylacetone at a molar ratio of 1 / 0.5 / 1 was used instead of catalyst B. . Yield 5%.
According to the GPC analysis (130 ° C.), Mn = 5,000 and Mw = 15,000.
[0070]
Comparative Example 7
Instead of catalyst B, 2,5-dimethyltetrahydrofuran was prepared by the method described in Example 8 except that a 0.1 M toluene solution of a catalyst obtained by mixing triethylaluminum / water / acetylacetone at a molar ratio of 1 / 0.5 / 1 was used. Polymerized. No solid matter was obtained after the reprecipitation operation. Yield 0%
[0071]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the high polymerization degree polyether useful in the cosmetics field | area and a chemicals field | area can be provided easily with a sufficient yield.

Claims (3)

Formula (I)

{In the formula, a rare earth element selected from M: Sc, Y or a lanthanoid is shown.
L ¹ , L ² , L ^{3 are the} same or different and represent oxygen or nitrogen-bonded ligands. }
In the presence of a rare earth metal compound and an organoaluminum compound, epoxides represented by general formulas (II) to (V) ( excluding epoxides represented by the following general formulas (ii) to (iv)) preparation of polyether polymerizing monomer components comprising at least one).

{Wherein R ¹ represents a hydrogen atom, or a halogen atom, diazo group, hydroxyl group, nitrile group, ammonium group, nitro group, isocyanate group, amino group, mercapto group, carboxyl group, carboxylate group as a substituent, Aldehyde group, carbonyl group, ester group, ether group, amide group, sulfide group, sulfenyl group, sulfonyl group, phosphine group, hypophosphorous acid group, phosphorous acid group, phosphoric acid group, phosphonium group, silyl group and siloxy A hydrocarbon group having 1 to 50 carbon atoms which may have a substituent selected from a group (hereinafter referred to as “substituent of the present invention”), an acyl group having 1 to 30 carbon atoms, It represents an alkyl sulfonyl group or arylsulfonyl group having 6 to 30 carbon atoms having 1 to 30 carbon atoms, or - a group represented by (AO) n-R ^3. Here, R ³ is a hydrocarbon group having 1 to 30 carbon atoms, a fluoroalkyl group having 1 to 30 carbon atoms, a fluoroalkenyl group having 1 to 30 carbon atoms or a carbon number which may have a substituent of the present invention. It represents a 6-30 fluoroaryl group or a siloxysilyl group having 1-50 silicon atoms. A represents an alkylene group having 2 to 3 carbon atoms, and n represents a number having an average value of 1 to 1000. A part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group, acyl group, alkylsulfonyl group or arylsulfonyl group represented by R ¹ may be substituted with a fluorine atom.
R ² represents a substituent of the present invention that can be bonded to the epoxy ring, or has the same meaning as R ^1, and three R ² may be the same or different. However, the case where all of R ² are simultaneously hydrogen atoms is excluded. }

{In the formula, R ⁴ represents a hydrogen atom, a substituent of the present invention which can be bonded to an epoxy ring, or a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent of the present invention. Or an acyl group having 1 to 30 carbon atoms, an alkylsulfonyl group having 1 to 30 carbon atoms or an arylsulfonyl group having 6 to 30 carbon atoms, or-(AO) n-R ³ (R ³ , A and n have the same meaning as described above), and part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group, acyl group, alkylsulfonyl group, arylsulfonyl group are fluorine atoms. It may be substituted, and a plurality of R ⁴ may be the same or different. However, the case where all of R ⁴ are hydrogen atoms at the same time is excluded. In addition, when three of R ⁴ are hydrogen atoms, the other one is a hydrocarbon group having 1 to 50 carbon atoms having no substituent. }

(Wherein R ⁴ represents the same meaning as described above, and a plurality of R ⁴ may be the same or different.)

(Wherein R ⁴ represents the same meaning as described above, and a plurality of R ⁴ may be the same or different.)

[Wherein, R ¹¹ represents an optionally substituted hydrocarbon group having 1 to 500 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an alkylsulfonyl group having 1 to 30 carbon atoms. Alternatively, it represents an arylsulfonyl group having 6 to 30 carbon atoms, or a group represented by — (A ¹ O) _n1 —R ²¹ .
Here, R ²¹ represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroaryl group having 6 to 30 carbon atoms, or 1 silicon atom. ˜50 siloxysilyl groups. A ¹ represents an alkylene group having 2 to 3 carbon atoms. n1 represents a number from 1 to 1000. ]

[Wherein R ³¹ represents an optionally substituted fluoroalkyl group having 1 to 30 carbon atoms, a fluoroalkenyl group, or a fluoroaryl group having 6 to 30 carbon atoms.
a1: The number of 0-20 is shown. ]

[Wherein, R ^{41 is the} same or different and represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms or a siloxy group having 1 to 200 silicon atoms.
G ¹ represents an optionally substituted alkylene group having 1 to 20 carbon atoms or an arylene group.
b1: A number of 1 to 500 is shown as an average value of a plurality of numbers, or an integer of 1 to 20 is shown as a single number.
p1: The number of 0 or 1 is shown. ] A polyether represented by any one of the general formulas (VI) to (IX) obtained by the production method according to claim 1 .

{Wherein, R ^1, R ^2: the same meanings as R ^1, R ² in the general formula (II). However, at least one of R ² is the substituent of the present invention or a hydrocarbon group having 6 or more carbon atoms, which can be bonded to the epoxy ring.
a: Number with an average value of 10 or more. }

{In the formula, R ⁴ represents the same meaning as R ⁴ in the general formula (III). However, at least one of R ⁴ is a substituent of the present invention or a hydrocarbon group having 6 or more carbon atoms that can be bonded to the epoxy ring.
b: Number with an average value of 10 or more. }

{Wherein R ⁴ represents the same meaning as R ⁴ in formula (IV). However, at least one of R ⁴ is a substituent of the present invention or a hydrocarbon group having 6 or more carbon atoms that can be bonded to the epoxy ring.
d: Number with an average value of 10 or more. }

{In the formula, R ⁴ represents the same meaning as R ⁴ in the general formula (V). However, at least one of R ⁴ is a substituent of the present invention or a hydrocarbon group having 6 or more carbon atoms that can be bonded to the epoxy ring.
e: A number having an average value of 10 or more. } A polyether represented by the general formula (X) obtained by the production method according to claim 1 .

{In the formula, X and Y represent any two of the structural units represented by the general formulas (VI) to (IX) and other epoxides or other anionically polymerizable structural units. However, at least one of X and Y is assumed to have a structural unit represented by general formulas (VI) to (IX), and the case where X and Y are the same is excluded.
f, g: Numbers each having an average value of 10 or more. }