JP2004161986A - Living polymer of methacrylic acid (alkyl-substituted) aziridinylalkyl ester and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a living polymer of a methacrylic acid aziridinylalkyl ester having a narrow molecular weight distribution which is a polymer of methacrylic acid alkyl ester having an alkyleneimine group at a side chain and to provide a method for producing the living polymer and to provide a block copolymer having a methacrylic acid aziridinylalkyl ester segment. <P>SOLUTION: The methacrylic acid aziridinylalkyl ester has a recurring unit represented by general formula (I) (wherein R<SP>1</SP>to R<SP>4</SP>are each a hydrogen atom or a 1-3C alkyl group and they may be each the same or different; m is an integer of 1-8) and has 1,000-100,000 number-average molecular weight (Mn) and ≤1.20 molecular weight distribution (Mw/Mn wherein Mw is weight average molecular weight). <P>COPYRIGHT: (C)2004,JPO

Description

（Ｒ^１〜Ｒ^４はそれぞれ水素原子又は炭素数１〜６のアルキル基であって、それぞれ同じであっても異なってもよい。ｍは１〜８の整数である。）、
（２）前記リビングポリマーのＲ^１〜Ｒ^４が水素原子であり、かつ、ｍが２である上記（１）のメタクリル酸アジリジニルアルキルエステルのリビングポリマー、
（３）前記一般式（Ｉ）で表される繰り返し単位をセグメントとして含有するブロック共重合体、
の製造に成功し、また
（４）下記一般式（II）で表されるメタクリル酸（アルキル置換）アジリジニルアルキルエステルを、対カチオンが１価のアルカリ金属イオンであるアニオン重合開始剤及びジアルキル亜鉛を含む開始剤系を用いてアニオン重合する上記（１）のリビングポリマーの製造方法
【化４】

（Ｒ^１〜Ｒ^４はそれぞれ水素原子又は炭素数１〜６のアルキル基であって、それぞれ同じであっても異なってもよい。ｍは１〜８の整数である。）、
（５）前記重合開始剤のアルカリ金属イオンがカリウムイオンである上記（４）記載のリビングポリマーの製造方法、
（６）前記一般式（II）で表されるメタクリル酸（アルキル置換）アジリジニルアルキルエステルを、アルキルリチウム塩と１，１−ジアリールエチレン及び塩化リチウムを含む開始剤系を用いてアニオン重合するリビングポリマーの製造方法、
が上記リビングポリマーを収率よく製造し得ることを見出し、本発明を完成するに至った。
【０００８】
【発明の実施の形態】
本発明に係る新規なリビングポリマーは、下記一般式（Ｉ）で表される繰り返し単位を有し、数平均分子量（Ｍｎ）が１，０００〜１００，０００であり、かつ、分子量分布（Ｍｗ／Ｍｎ、Ｍｗは重量平均分子量）が１．２０以下であるメタクリル酸（アルキル置換）アジリジニルアルキルエステルのリビングポリマーである。分子量分布が１．２０以下と狭いことにより、各種物性のばらつきが小さく種々の用途に応用展開が期待される。
【０００９】
【化５】

（Ｒ^１〜Ｒ^４はそれぞれ水素原子又は炭素数１〜６のアルキル基であって、それぞれ同じであっても異なってもよい。ｍは１〜８の整数である。）
【００１０】
該新規リビングポリマーは、下記一般式（II）で表されるメタクリル酸（アルキル置換）アジリジニルアルキルエステルの構造を選択することによって、Ｒ^１〜Ｒ^４及びｍを任意に選択することができるが、ポリマーの物理的性質やアジリジニル基の反応性制御等の観点から、Ｒ^１〜Ｒ^４はそれぞれ水素原子又は炭素数１〜６のアルキル基であり、ｍは１〜８の整数である必要がある。Ｒ^１〜Ｒ^４はそれぞれ同じでも異なってもよく、用途に応じて、または必要とするブロック共重合体に応じて適宜選択することができるが、アジリジニル基の高い反応性を発現させるとの観点からはＲ^１〜Ｒ^４が水素である場合が最も好ましい。また、ｍについても１〜８の整数から任意に選択可能であるが、ポリマーの安定性、リビングポリマーの製造の容易さ等を考慮すると、ｍは１〜４の範囲がより好ましく、特にはｍが２である場合が好ましい。
本発明におけるモノマーは、メタクリル酸メチルと（アルキル置換）アジリジニルアルコールとのエステル交換反応によって得ることができる。従って、（アルキル置換）アジリジニルアルコールの構造を変えることによって、所望のリビングポリマーを得ることができる。
【００１１】
【化６】

（Ｒ^１〜Ｒ^４はそれぞれ水素原子又は炭素数１〜６のアルキル基であって、それぞれ同じであっても異なってもよい。ｍは１〜８の整数である。）
【００１２】
以下に上記新規リビングポリマーの製造方法について詳細に説明する。
本発明ではアニオン重合によって該リビングポリマーを製造するが、対カチオンが１価のアルカリ金属イオンであるアニオン重合開始剤及びジアルキル亜鉛を含む開始剤系を用いてアニオン重合することを特徴とする。
対カチオンとなるアルカリ金属としては、カリウム、リチウム、ナトリウム、セシウム等が挙げられるがカリウム、リチウムが好ましく、特にカリウムが好ましい。アニオン重合開始剤は、具体的にはジフェニルメチルカリウム、ジフェニルメチルカリウムと１，１−ジフェニルエチレンの１：１付加物、クミルカリウムと１，１−ジフェニルエチレンの１：１付加物、１，１，４，４−テトラフェニルブタンジカリウム、トリフェニルメチルカリウム、フルオレニルカリウム、１，１−ジフェニルヘキシルリチウム、１，１−ジフェニル−３−メチルペンチルリチウム、１，１，４，４−テトラフェニルブタンジリチウム、ジフェニルメチルリチウム、トリフェニルメチルリチウム、フルオレニルリチウム等が挙げられるが、ジフェニルメチルカリウムが好ましい。
これらの重合開始剤の添加量は、目的とするポリマーの分子量を考慮して適宜決定されるが、一般式（II）で表されるメタクリル酸（アルキル置換）アジリジニルアルキルエステル１モルに対して０．０１〜１００ミリモルの範囲が好ましく、特には０．０５〜１０ミリモルの範囲が好ましい。
ジアルキル亜鉛としては、ジメチル亜鉛、ジエチル亜鉛、ジプロピル亜鉛、ジブチル亜鉛等があるが、中でもジエチル亜鉛が好ましい。該ジアルキル亜鉛の添加量としては、アニオン重合開始剤の添加量に対し５．０〜５０モル当量の範囲が好ましく、さらには１０〜２０モル当量の範囲が好ましい。
【００１３】
またアニオン重合の開始剤系として、アルキルリチウム塩と１，１−ジアリールエチレン及び塩化リチウムを含むものも好適に使用される。
ここでアルキルリチウム塩としてはメチルリチウム、エチルリチウム、ｎ−プロピルリチウム、ｉｓｏ−プロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、ｎ−ペンチルリチウム、ｓｅｃ−ペンチルリチウム、ｉｓｏ−ペンチルリチウム等が用いられるが、ｎ−ブチルリチウムやｓｅｃ−ブチルリチウムが好ましい。
また、１，１−ジアリールエチレンは、フェニル基、ナフチル基、アントラセニル基等の芳香環を有し、これらの芳香環にアルキル基やトリメチルシリル基等の置換基を有していてもよい。これらの中で１，１−ジフェニルエチレンが最も好ましい。
上記アルキルリチウム塩の添加量は、目的とするポリマーの分子量を考慮して適宜決定されるが、一般式（II）で表されるメタクリル酸（アルキル置換）アジリジニルアルキルエステル１モルに対して０．０１〜１００ミリモルの範囲が好ましく、特には０．０５〜１０ミリモルの範囲が好ましい。１，１−ジアリールエチレンの好ましい添加量はアルキルリチウム塩の添加量に対して１．０〜５．０モル当量の範囲、さらに好ましくは１．２〜２．５モル当量の範囲である。また塩化リチウムの好ましい添加量は、アルキルリチウム塩添加量の１．０〜１０．０モル当量の範囲、さらに好ましくは２．５〜５．０モル当量の範囲である。
【００１４】
本発明におけるアニオン重合の条件は、モノマーの種類、重合開始剤の種類、必要とされるリビングポリマーの重合度等によって、適宜選択されるが、通常はモノマー濃度０．０５〜２．０モル／リットルの範囲であることが好ましく、０．２〜１．０モル／リットルの範囲であることがさらに好ましい。重合温度は−１００℃〜１００℃の範囲であることが好ましく、−８０〜０℃の範囲であることがさらに好ましい。また、重合反応はアルゴンや窒素等の不活性ガス雰囲気下、あるいは減圧下で行うことができるが、１０^−３ｍｍＨｇ以下の減圧下で行うことが好ましく、１０^−６ｍｍＨｇ以下の減圧下で行うことがさらに好ましい。
尚、重合時間に関しては、モノマーの種類、重合開始剤の種類等によって異なるが、通常はポリマー収率が９５％以上となり、ポリマーが定量的に得られるに必要な時間重合を行う。具体的には１０分〜７２時間程度である。
また、本リビング重合に適当な溶媒としては、テトラヒドロフラン，ジオキサン，ジエチルエーテル等のエーテル類や、ｎ−ヘキサン，ｎ−ヘプタン等の脂肪族炭化水素類、シクロヘキサン，メチルシクロヘキサン等の脂環式炭化水素類、ベンゼン，トルエン等の芳香族炭化水素類等が挙げられるが、中でも極性モノマーの重合制御の観点からテトラヒドロフラン、テトラヒドロフランと脂肪族炭化水素類との混合溶媒、テトラヒドロフランと芳香族炭化水素類との混合溶媒等が好適に用いられる。
【００１５】
本発明のリビングポリマーとアニオン重合可能な他のモノマーとの反応により、一般式（Ｉ）で表される繰り返し単位をセグメントとして含有するブロック共重合体を得ることができる。他のモノマーの例としては、メタクリル酸メチル，メタクリル酸エチル，メタクリル酸ｉｓｏ−プロピル，（メタ）アクリル酸ｔｅｒｔ−ブチル，メタクリル酸グリシジル等の（メタ）アクリル酸エステル、スチレンやα−メチルスチレンなどのスチレン誘導体、ブタジエン、イソプレン等が挙げられる。尚、ブロック共重合体の重合は、前述のアニオン重合と同様の条件で行うことができる。
【００１６】
【実施例】
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
実施例１
（１）モノマー（メタクリル酸２−（１−アジリジニル）エチル）の合成
一体型の蒸留装置にメタクリル酸メチル２４．８０グラム（２４８ミリモル）と１−（２−ヒドロキシルエチル）エチレンイミン６．５６グラム（７５．３ミリモル）を仕込み、水素化ナトリウム１０ミリグラム（０．４２ミリモル）を添加した。その後オイルバスにて６０℃に加熱し、１５０ｍｍＨｇの減圧下、生成するメタノールを除去しながら、エステル交換反応を１時間行った。その後徐々に減圧し、６０ｍｍＨｇで未反応のメタクリル酸メチルを留去した。更に減圧度を５ｍｍＨｇまで下げ、未反応の１−（２−ヒドロキシルエチル）エチレンイミンを留去した。収量は４．５５ｇ（収率；３９％）であった。
【００１７】
（２）モノマーの精製
上記方法で合成したモノマーをトリエチルアミンでコンディショニングしたシリカゲルと、展開溶媒としてジエチルエーテル／トリエチルアミン混合溶媒（トリエチルアミン２．０モル％含有）を用い、カラムクロマトグラフィーにより精製した。次いで、水素化カルシウムの存在下で１２時間攪拌し、減圧蒸留してさらに精製した。
該精製物について、^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲ測定、並びに元素分析を行った。図１に^１Ｈ−ＮＭＲの測定結果、図２に^１３Ｃ−ＮＭＲの測定結果を示す。^１Ｈ−ＮＭＲチャートのピークに付されたａ，ｂ，ｃ等は、該チャートに記された構造式の添字ａ，ｂ，ｃ等が付された水素原子に帰属されるものであり、また^１３Ｃ−ＮＭＲチャートのピークに付された１，２，３等の数字は、該チャートに記された構造式の添字１，２，３等が付された炭素原子に帰属されるものである。また、得られた精製物の元素分析の結果、炭素６１．９１％（計算値；６１．９５％）、水素８．７０％（計算値；８．４５％）、窒素９．０３％（計算値；８．９０％）であった。
これらのＮＭＲチャート及び元素分析の結果から、得られた精製物がメタクリル酸２−（１−アジリジニル）エチルであることが確認された。
次に、精製されたメタクリル酸２−（１−アジリジニル）エチル４．６６グラム（３０．１ミリモル）をテトラヒドロフラン５．０ミリリットル、水素化カルシウム０．８９グラムと混合し、攪拌子とともにブレークシールを溶接したガラス容器に溶封した。この混合液を１２時間攪拌し、さらに高真空ラインで蒸留精製した。精製されたメタクリル酸２−（１−アジリジニル）エチル４．４５グラム（２８．７ミリモル）をテトラヒドロフランで希釈し、０．４５モル／リットルの溶液を調製した。この溶液をアンプルに分取し、溶封してアニオン重合に供した。
【００１８】
（３）アニオン重合
アニオン重合は前記メタクリル酸２−（１−アジリジニル）エチルのテトラヒドロフラン溶液１２．８４ミリリットル（モノマー量；５．７７ミリモル）に、アニオン重合開始剤として対カチオンが１価のアルカリ金属イオンであるジフェニルメチルカリウムのテトラヒドロフラン溶液３．９６ミリリットル（ジフェニルメチルカリウム；０．０９３９ミリモル）及びジアルキル亜鉛であるジエチル亜鉛のテトラヒドロフラン溶液２．１７ミリリットル（ジエチル亜鉛；１．６０ミリモル、ジフェニルメチルカリウムの１７モル当量に該当）を添加し、ブレークシール法により、１×１０^−６ｍｍＨｇの減圧下、−７８℃で重合を１時間行い、リビングポリマーを得た。その後、ガラス製重合容器を開封し、メタノールを少量添加して、重合を停止させた。ついで、得られた重合溶液を多量のｎ−ヘキサン中に注ぎ込み、ポリマーを沈殿させた。この沈殿したポリマーを濾別し、乾燥した。ポリマーの収率は９９％であり、さらに未精製の重合溶液の^１Ｈ−ＮＭＲ測定を行ったところ、図１に示す構造式の添字ａ，ｂに帰属されるモノマーの水素原子のシグナルがほぼ完全に消失しており、また図１に示す構造式の添字ｄに帰属されるモノマーの水素原子のシグナルの積分値と図３に示す構造式の添字ｃに帰属されるポリマーの水素原子のシグナルの積分値の比から、モノマーの転化率は９９％であった。
【００１９】
（４）数平均分子量と分子量分布の測定
上記方法で得られたポリマーをテトラヒドロフランに溶解し（濃度１０ミリグラム／ミリリットル）、数平均分子量と分子量分布をゲル浸透クロマトグラフィー（ＧＰＣ）法により測定した。尚、分子量分布はＧＰＣ法により測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）である。得られた結果を第２表に示す。分子量分布は１．０７であり、分子量分布の狭いポリマーを短い重合時間で定量的に得ることができた。
【００２０】
（５）ポリマーの精製及び構造解析
上記方法により得られたポリマーを７．０質量％のポリマー濃度となるようにテトラヒドロフランに溶解させ、この溶液を１０倍容量のｎ−ヘキサン中に注ぎ込み、ポリマーを再沈殿精製した。沈殿したポリマーを濾別し、１５質量％のポリマー濃度となるようにベンゼンに溶解させ、凍結乾燥を行って得られたポリマーについて、^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲ測定を行った。図３に^１Ｈ−ＮＭＲの測定結果、図４に^１３Ｃ−ＮＭＲの測定結果を示す。ここで添字ａ，ｂ，ｃ等及び添字１，２，３等は図１及び図２で説明したのと同様である。^１Ｈ−ＮＭＲ，^１３Ｃ−ＮＭＲのチャートから得られたポリマーが一般式（Ｉ）において、Ｒ^１〜Ｒ^４が水素原子であり、かつ、ｍが２であるメタクリル酸２−（１−アジリジニル）エチルエステルのポリマーであることが確認された。
【００２１】
実施例２
実施例１で合成、精製したモノマーを用い、モノマー量、重合開始剤の添加量、ジエチル亜鉛の添加量及び重合時間を第１表に示すものに変えた以外は実施例１と同様にしてリビングポリマーの重合を行った。メタノールを少量添加して重合を停止させて得られたポリマーの^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲを測定した結果、図３及び図４と同様のチャートを示し、得られたリビングポリマーが実施例１と同様の構造を有するリビングポリマーであることが確認された。また、該リビングポリマーの収率及び転化率を第２表に示す。
実施例１と同様に分子量分布は１．０７と良好な値を示し、かつ重合時間も短時間で定量的に目的とするリビングポリマーが得られた。
【００２２】
実施例３
実施例１で合成、精製したモノマーのテトラヒドロフラン溶液７．０３ミリリットル（メタクリル酸２−（１−アジリジニル）エチル；３．１６ミリモル）、重合開始剤としてアルキルリチウム塩であるｓｅｃ−ブチルリチウムのｎ−ヘプタン溶液２．８１ミリリットル（ｓｅｃ−ブチルリチウム；０．０８６８ミリモル）、１，１−ジアリールエチレンである１，１−ジフェニルエチレンのテトラヒドロフラン溶液２．３２ミリリットル（１，１−ジフェニルエチレン；０．１４３ミリモル）及び塩化リチウムのテトラヒドロフラン溶液２．６９ミリリットル（塩化リチウム；０．２９９ミリモル）とし、重合時間を４８時間とした以外は実施例１と同様にしてリビングポリマーの重合を行った。実施例１と同様に得られたポリマーの^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲを測定した結果、図３及び図４と同様のチャートを示し、得られたリビングポリマーが実施例１と同様の構造を有するリビングポリマーであることが確認された。また、該リビングポリマーの収率及び転化率を第２表に示す。
重合速度がやや遅く定量的にポリマーを得るのには時間がかかるものの、高収率で分子量分布が１．０４と狭いリビングポリマーが得られた。
【００２３】
比較例１
実施例１で合成、精製したモノマーを用い、モノマー量、重合開始剤の添加量を第１表に示すものに変え、ジエチル亜鉛を添加しなかったこと以外は実施例１と同様にしてアニオン重合を行った。得られたポリマーの^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲを測定した結果、図３及び図４と同様のスペクトルが観測され、得られたポリマーが実施例１と同様の化学構造を有することが確認された。また、該ポリマーの収率及び転化率を第２表に示す。
重合は１時間以内に完結したが、得られたポリマーの分子量分布は１．２４と広かった。
【００２４】
比較例２
実施例１で合成、精製したモノマーを用い、モノマー量、重合開始剤の添加量を第１表に示すものに変え、塩化リチウムを添加しなかったこと以外は実施例３と同様にしてアニオン重合を行った。得られたポリマーの^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲを測定した結果、図３及び図４と同様のスペクトルが観測され、得られたポリマーが実施例１と同様の化学構造を有することが確認された。また、該ポリマーの収率及び転化率を第２表に示す。
重合は１時間以内に完結したが、得られたポリマーの分子量分布は２．１９と広かった。
【００２５】
比較例３
三方コック付き重合管に、実施例１で合成、精製したモノマー１４．６ミリモルと溶媒としてベンゼン３０ミリリットルを入れ、重合開始剤としてアゾイソブチロニトリル（ＡＩＢＮ）０．２７４ミリモルを添加し、１×１０^−３ｍｍＨｇの減圧下、７０℃でラジカル重合を行った。重合開始から１４時間の後に液体窒素で重合溶液を凍結して重合を停止させた。その後、得られた重合溶液を多量のｎ−ヘキサン中に注ぎ込み、ポリマーを沈殿させた。この沈殿したポリマーを濾別し、乾燥した。収率は９５％であり、モノマーの転化率は９１％であった。
次いで、乾燥させたポリマーをテトロヒドロフランに再度溶解させ、多量のｎ−ヘキサン中に注ぎ込み、ポリマーを再沈殿させた。沈殿したポリマーをベンゼンに溶解させ、凍結乾燥を行って得られたポリマーの^１Ｈ−ＮＭＲ及び^１３Ｃ−ＮＭＲを測定した結果、図３及び図４と同様のスペクトルが観測され、得られたポリマーが実施例１と同様の化学構造を有することが確認された。また、該ポリマーの収率及び転化率を第２表に示す。
得られたポリマーの分子量分布は３．７７と広かった。
【００２６】
【表１】

【００２７】
＊１ Ｐｈ_２ＣＨＫ；ジフェニルメチルカリウム
＊２ ｓｅｃ−ＢｕＬｉ；ｓｅｃ−ブチルリチウム
＊３ ＡＩＢＮ；アゾビスイソブチロニトリル
＊４ ＤＰＥ；１，１−ジフェニルエチレン
＊５ ＬｉＣｌ；塩化リチウム
＊６ Ｅｔ_２Ｚｎ；ジエチル亜鉛
【００２８】
【表２】

【００２９】
＊７ 計算値；開始剤の末端官能基部分とモノマー／開始剤モル比から算出される分子量の計算値
＊８ 実測値；開始剤の末端官能基部分とポリマーの繰り返し構造単位に含まれる官能基部分との^１Ｈ−ＮＭＲ測定から得られる面積比から算出した分子量の実測値
＊９ 数平均分子量及び分子量分布；移動相としてＮ，Ｎ−ジメチルホルムアミド（ヨウ化リチウム添加品０．０１モル／リットル）を用い、カラム温度４０℃、送液速度１．０ミリリットル／分で測定し、標準ポリスチレンの分子量を用いて換算した値（ＧＰＣ装置；高速ＧＰＣ装置「ＨＬＣ−８１２０ＧＰＣ」（東ソー（株）製）、高速カラム；ＴＳＫ ｇｕａｒｄ ｃｏｌｕｍｎ Ｈ_ＸＬ−Ｈ、ＴＳＫ ｇｅｌ ＧＭＨ_ＸＬ、ＴＳＫ ｇｅｌ ＧＭＨ_ＸＬ、及びＴＳＫ ｇｅｌ Ｇ２０００Ｈ_ＸＬ（以上全て東ソー（株）製）をこの順序に連結して使用、検出器；示差屈折計及び紫外可視検出器（波長；２５４ｎｍ））
＊１０ ラジカル重合体の実測分子量は上記＊９に準じて測定
【００３０】
実施例４
（１）メタクリル酸メチルの精製
市販のメタクリル酸メチル（東京化成工業（株））２５．０グラム（０．２５モル）を５．０質量％水酸化ナトリウム水溶液５０ミリリットル、脱イオン水５０ミリリットルで洗浄して重合禁止剤を取り除いた後、無水硫酸マグネシウム３．６グラムを加えて１２時間脱水させた。脱水剤を濾別した後、水素化カルシウム２．５グラムを加え、２４時間乾燥させた。次いで水素化カルシウムをが存在したまま、４９．１〜４９．５℃、１１３ｍｍＨｇで減圧蒸留を行い、脱水メタクリル酸メチル２３．３グラム（０．２３モル）を得た。
脱水メタクリル酸メチル７．３６グラム（７３．６ミリモル）と水素化カルシウム１．０６グラム、ｎ−ヘプタン１１．１ミリリットルをブレークシールを備えた５０ミリリットル丸底フラスコに溶封した。この混合溶液を１２時間攪拌した後、高真空ラインで蒸留精製した。さらにトリ（ｎ−オクチル）アルミニウム１．４１ミリモルの存在下、高真空ラインで蒸留精製して、メタクリル酸メチル６．５７グラム（６５．７ミリモル）を得た。得られたメタクリル酸メチルをテトラヒドロフランで希釈し、０．６９モル／リットルの溶液を調製した。この溶液をブレークシールを備えたアンプルに分取して溶封し、アニオン重合を行った。
【００３１】
（２）ブロック共重合
高真空下で溶封した重合容器にブレークシールを介して、アニオン重合開始剤であるジフェニルメチルカリウムのテトラヒドロフラン溶液５．５９ミリリットル（ジフェニルメチルカリウム；０．１３０ミリモル）を移し、−７８℃に冷却し、以後重合停止まで該温度を保持した。
次に、ジエチル亜鉛のテトラヒドロフラン溶液４．２７ミリリットル（ジエチル亜鉛；１．６８ミリモル）を加え、２０分間反応させた後、実施例１と同様に精製して、アンプルに溶封されたメタクリル酸２−（１−アジリジニル）エチルのテトラヒドロフラン溶液１２．４７ミリリットル（メタクリル酸２−（１−アジリジニル）エチル；５．７６ミリモル）を加え、十分に攪拌しながら２０分間重合を行い、メタクリル酸２−（１−アジリジニル）エチルのリビングポリマーを得た。
続いて精製したメタクリル酸メチルのテトラヒドロフラン溶液１２．０３ミリリットル（メタクリル酸メチル；４．１８ミリモル）を添加し、十分に攪拌しながら１５分間重合を行った後、メタノールのテトラヒドロフラン溶液５．８０ミリリットル（メタノール；１８．４ミリモル）を添加して、重合を停止させた。
この重合溶液をエバポレーターを用いて濃縮した後、多量のｎ−ヘキサン中に注ぎ込み、ポリマー（ブロック共重合体）を沈殿させ、濾別乾燥させた。ポリマーの収率は９６％であった。また未精製の重合溶液の^１Ｈ−ＮＭＲ測定結果より、メタクリル酸２−（１−アジリジニル）エチルとメタクリル酸メチルの転化率は共に９９％であることが確認された。得られたポリマーの数平均分子量は計算値が１０，０００、実測値が１２，０００であり、ほぼ一致した。また分子量分布は図５に示すように、１．０５であった。
【００３２】
（３）ポリマーの精製及び構造解析
上記方法により得られたポリマーを７．０質量％のポリマー濃度となるようにテトラヒドロフランに溶解させ、この溶液を１０倍容量のｎ−ヘキサン中に注ぎ込み、ポリマーを再沈殿精製した。沈殿したポリマーを濾別し、１５質量％のポリマー濃度となるようにベンゼンに溶解させ、凍結乾燥を行って得られたポリマーについて、^１Ｈ−ＮＭＲ測定を行った。図６に^１Ｈ−ＮＭＲの測定結果を示す。ここで添字ａ，ｂ，ｃ等は図１で説明したのと同様である。^１Ｈ−ＮＭＲのチャートから得られたポリマーがメタクリル酸２−（１−アジリジニル）エチルとメタクリル酸メチルのブロックポリマーであることが確認された。
【００３３】
【発明の効果】
本発明によれば、側鎖にアルキレンイミン基を有するメタクリル酸アルキルエステルのポリマーであって、分子量分布の狭いメタクリル酸（アルキル置換）アジリジニルアルキルエステルのリビングポリマーを高収率で得ることができる。
該リビングポリマーは、アルキレンイミン基が高い反応性を有することから、粘着剤、接着剤、塗料の架橋剤、レジスト材料、コーティング剤、フィルム製膜の分野での架橋剤、主ポリマー、ベース樹脂等の原材料等として広範な応用が期待できる
【図面の簡単な説明】
【図１】実施例１のモノマーの^１Ｈ−ＮＭＲチャートである。
【図２】実施例１のモノマーの^１３Ｃ−ＮＭＲチャートである。
【図３】実施例１のリビングポリマーをメタノールで重合停止させたものの^１Ｈ−ＮＭＲチャートである。
【図４】実施例１のリビングポリマーをメタノールで重合停止させたものの^１３Ｃ−ＮＭＲチャートである。
【図５】実施例４の共重合体のＧＰＣ曲線である。
【図６】実施例４の共重合体をメタノールで重合停止させたものの^１Ｈ−ＮＭＲチャートである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a living polymer of a methacrylic acid ester having an (alkyl-substituted) aziridinyl group, a block copolymer thereof, and a method for producing the living polymer. More specifically, the present invention relates to a living polymer having a narrow molecular weight distribution, a block copolymer thereof, and The present invention relates to a method for producing these in good yield.
[0002]
[Prior art]
Living polymers having an alkyleneimine group in the side chain have a high reactivity because the alkyleneimine group has a high reactivity, and thus, a crosslinking agent in the fields of pressure-sensitive adhesives, adhesives, paint crosslinkers, resist materials, coating agents, and film forming. It is a polymer that can be expected to be widely applied as raw materials such as agents, main polymers and base resins.
Further, since the active terminal carbanion has high reactivity, it has an advantage that synthesis of a block copolymer, a terminal functionalized polymer, a graft polymer, a star polymer and the like is easy.
When the living polymer is used for the above-mentioned applications, it is required that the molecular weight distribution is close to monodispersion. This is because, in general, the molecular weight distribution is close to monodispersion, whereby various properties such as a glass transition temperature, a melting point, an intrinsic viscosity, solubility, and light transmittance become clear, and a detailed material design can be performed.
[0003]
Conventionally, polymers of methacrylic esters have been used industrially for a long time because they can be easily obtained by radical polymerization. Currently, polymethacrylic esters having various functional groups have been synthesized.
A polymer having an alkyleneimine group in the side chain can also be obtained by radical polymerization, but the molecular weight distribution of the polymer is about 3 to 10, and only a polymer having a wide molecular weight distribution has been obtained. Therefore, the physical properties of the obtained polymer vary, and the above-mentioned detailed material design and the like are difficult, and the polymer cannot be practically applied to various uses.
Moreover, it is difficult to control the reaction by the conventional radical polymerization method, and it is not possible to obtain a block copolymer having a strictly controlled primary structure, and it is difficult to obtain a block copolymer quantitatively. Met.
[0004]
On the other hand, anionic living polymerization can generally control the chemical structure and molecular weight, and can obtain a polymer having a narrow molecular weight distribution (see, for example, Patent Document 1). However, regarding a polymer having an alkyleneimine group in a side chain, Since the reactivity of the side chain group is high, side reactions are likely to occur and it is difficult to control the side reactions, and no clear primary structure has been obtained so far.
[0005]
[Patent Document 1]
JP-A-4-15205 (Claims)
[0006]
[Problems to be solved by the invention]
The present invention relates to a polymer of a methacrylic acid (alkyl-substituted) alkyl ester having an alkyleneimine group in a side chain, which has a narrow molecular weight distribution. An object of the present invention is to provide a polymer and a method for producing the living polymer by anionic living polymerization, and to provide a block copolymer having a methacrylic acid (alkyl-substituted) aziridinylalkyl ester segment.
[0007]
[Means for Solving the Problems]
The present inventors have conducted various studies to achieve the above object, and as a result,
(1) It has a repeating unit represented by the following general formula (I), has a number average molecular weight (Mn) of 1,000 to 100,000, and has a molecular weight distribution distribution (Mw / Mn, Mw is weight average Living polymer of methacrylic acid (alkyl-substituted) aziridinyl alkyl ester having a molecular weight of 1.20 or less
Embedded image

(R ¹ ~ R ⁴ Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. m is an integer of 1 to 8. ),
(2) R of the living polymer ¹ ~ R ⁴ Is a hydrogen atom, and m is 2, a living polymer of the aziridinyl methacrylate alkyl ester of the above (1),
(3) a block copolymer containing the repeating unit represented by the general formula (I) as a segment,
Successfully manufactured
(4) A methacrylic acid (alkyl-substituted) aziridinyl alkyl ester represented by the following general formula (II) is used as an anion polymerization initiator whose counter cation is a monovalent alkali metal ion and an initiator system containing dialkyl zinc. Method for producing living polymer of the above (1) which is anionically polymerized using
Embedded image

(R ¹ ~ R ⁴ Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. m is an integer of 1 to 8. ),
(5) The method for producing a living polymer according to the above (4), wherein the alkali metal ion of the polymerization initiator is a potassium ion.
(6) Anionic polymerization of the methacrylic acid (alkyl-substituted) aziridinyl alkyl ester represented by the general formula (II) using an alkyl lithium salt and an initiator system containing 1,1-diarylethylene and lithium chloride. A method for producing a living polymer,
Have found that the living polymer can be produced in good yield, and have completed the present invention.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The novel living polymer according to the present invention has a repeating unit represented by the following general formula (I), has a number average molecular weight (Mn) of 1,000 to 100,000, and has a molecular weight distribution (Mw / Mn and Mw are living polymers of methacrylic acid (alkyl-substituted) aziridinylalkyl esters having a weight average molecular weight of 1.20 or less. When the molecular weight distribution is as narrow as 1.20 or less, variations in various physical properties are small, and application development to various uses is expected.
[0009]
Embedded image

(R ¹ ~ R ⁴ Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. m is an integer of 1 to 8. )
[0010]
By selecting the structure of methacrylic acid (alkyl-substituted) aziridinylalkyl ester represented by the following general formula (II), ¹ ~ R ⁴ And m can be arbitrarily selected, but from the viewpoints of physical properties of the polymer and control of the reactivity of the aziridinyl group, R ¹ ~ R ⁴ Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, respectively, and m needs to be an integer of 1 to 8. R ¹ ~ R ⁴ May be the same or different, and can be appropriately selected depending on the application or the required block copolymer. From the viewpoint of expressing the high reactivity of the aziridinyl group, R ¹ ~ R ⁴ Is most preferably hydrogen. Also, m can be arbitrarily selected from an integer of 1 to 8, but in consideration of the stability of the polymer, the easiness of production of a living polymer, and the like, m is more preferably in the range of 1 to 4, and particularly preferably m Is preferably 2.
The monomer in the present invention can be obtained by a transesterification reaction between methyl methacrylate and (alkyl-substituted) aziridinyl alcohol. Therefore, by changing the structure of the (alkyl-substituted) aziridinyl alcohol, a desired living polymer can be obtained.
[0011]
Embedded image

(R ¹ ~ R ⁴ Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. m is an integer of 1 to 8. )
[0012]
Hereinafter, the method for producing the novel living polymer will be described in detail.
In the present invention, the living polymer is produced by anionic polymerization, and is characterized in that anionic polymerization is performed using an anionic polymerization initiator whose counter cation is a monovalent alkali metal ion and an initiator system containing dialkylzinc.
Examples of the alkali metal serving as a counter cation include potassium, lithium, sodium, and cesium. Potassium and lithium are preferable, and potassium is particularly preferable. Specific examples of the anionic polymerization initiator include diphenylmethyl potassium, a 1: 1 adduct of diphenylmethyl potassium and 1,1-diphenylethylene, a 1: 1 adduct of cumyl potassium and 1,1-diphenylethylene, 4,4-tetraphenylbutane dipotassium, triphenylmethyl potassium, fluorenyl potassium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,1,4,4-tetraphenyl butane Examples thereof include dilithium, diphenylmethyllithium, triphenylmethyllithium, and fluorenyllithium, with diphenylmethylpotassium being preferred.
The addition amount of these polymerization initiators is appropriately determined in consideration of the molecular weight of the target polymer, and is based on 1 mol of methacrylic acid (alkyl-substituted) aziridinyl alkyl ester represented by the general formula (II). Is preferably in the range of 0.01 to 100 mmol, particularly preferably in the range of 0.05 to 10 mmol.
Examples of the dialkyl zinc include dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc and the like, and among them, diethyl zinc is preferable. The addition amount of the dialkyl zinc is preferably in the range of 5.0 to 50 molar equivalents, more preferably 10 to 20 molar equivalents, based on the addition amount of the anionic polymerization initiator.
[0013]
As the initiator system for anionic polymerization, those containing an alkyl lithium salt, 1,1-diaryl ethylene and lithium chloride are also preferably used.
Here, as the alkyl lithium salt, methyl lithium, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, sec-pentyl lithium, iso- Pentyl lithium or the like is used, and n-butyl lithium and sec-butyl lithium are preferred.
Further, 1,1-diarylethylene has an aromatic ring such as a phenyl group, a naphthyl group, and an anthracenyl group, and these aromatic rings may have a substituent such as an alkyl group and a trimethylsilyl group. Of these, 1,1-diphenylethylene is most preferred.
The amount of the alkyl lithium salt to be added is appropriately determined in consideration of the molecular weight of the target polymer, and is based on 1 mol of methacrylic acid (alkyl-substituted) aziridinyl alkyl ester represented by the general formula (II). The range is preferably 0.01 to 100 mmol, particularly preferably 0.05 to 10 mmol. The preferable addition amount of 1,1-diarylethylene is in the range of 1.0 to 5.0 molar equivalents, more preferably in the range of 1.2 to 2.5 molar equivalents, based on the addition amount of the alkyl lithium salt. The preferable addition amount of lithium chloride is in the range of 1.0 to 10.0 molar equivalents, more preferably in the range of 2.5 to 5.0 molar equivalents of the added amount of the alkyl lithium salt.
[0014]
The conditions of the anionic polymerization in the present invention are appropriately selected depending on the type of the monomer, the type of the polymerization initiator, the required degree of polymerization of the living polymer, and the like, but usually the monomer concentration is 0.05 to 2.0 mol /. It is preferably in the range of liters, more preferably in the range of 0.2 to 1.0 mol / l. The polymerization temperature is preferably in the range of -100C to 100C, more preferably in the range of -80C to 0C. The polymerization reaction can be carried out under an atmosphere of an inert gas such as argon or nitrogen or under reduced pressure. ^-3 It is preferably performed under reduced pressure of not more than mmHg, ^-6 More preferably, the reaction is performed under reduced pressure of not more than mmHg.
The polymerization time varies depending on the type of the monomer, the type of the polymerization initiator, and the like. However, usually, the polymer yield is 95% or more, and the polymerization is performed for a time necessary for obtaining the polymer quantitatively. Specifically, it is about 10 minutes to 72 hours.
Suitable solvents for the present living polymerization include ethers such as tetrahydrofuran, dioxane and diethyl ether; aliphatic hydrocarbons such as n-hexane and n-heptane; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. And aromatic hydrocarbons such as benzene and toluene. Among them, tetrahydrofuran, a mixed solvent of tetrahydrofuran and aliphatic hydrocarbons, and a mixture of tetrahydrofuran and aromatic hydrocarbons from the viewpoint of controlling the polymerization of polar monomers. A mixed solvent or the like is suitably used.
[0015]
The block copolymer containing the repeating unit represented by the general formula (I) as a segment can be obtained by reacting the living polymer of the present invention with another monomer capable of anion polymerization. Examples of other monomers include (meth) acrylates such as methyl methacrylate, ethyl methacrylate, iso-propyl methacrylate, tert-butyl (meth) acrylate, glycidyl methacrylate, styrene and α-methylstyrene. Styrene derivatives, butadiene, isoprene and the like. The polymerization of the block copolymer can be performed under the same conditions as in the above-described anionic polymerization.
[0016]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
(1) Synthesis of monomer (2- (1-aziridinyl) ethyl methacrylate)
An integrated distillation apparatus was charged with 24.80 g (248 mmol) of methyl methacrylate and 6.56 g (75.3 mmol) of 1- (2-hydroxylethyl) ethyleneimine, and 10 mg (0.42 g) of sodium hydride. Mmol) was added. Thereafter, the mixture was heated to 60 ° C. in an oil bath, and a transesterification reaction was performed for 1 hour under a reduced pressure of 150 mmHg while removing generated methanol. Thereafter, the pressure was gradually reduced, and unreacted methyl methacrylate was distilled off at 60 mmHg. The degree of reduced pressure was further reduced to 5 mmHg, and unreacted 1- (2-hydroxylethyl) ethyleneimine was distilled off. The yield was 4.55 g (yield; 39%).
[0017]
(2) Purification of monomer
The monomer synthesized by the above method was purified by column chromatography using silica gel conditioned with triethylamine and a mixed solvent of diethyl ether / triethylamine (containing 2.0 mol% of triethylamine) as a developing solvent. Then, the mixture was stirred for 12 hours in the presence of calcium hydride, and further purified by distillation under reduced pressure.
About the purified product, ¹ H-NMR and ^Thirteen C-NMR measurement and elemental analysis were performed. In FIG. ¹ H-NMR measurement results are shown in FIG. ^Thirteen The measurement results of C-NMR are shown. ¹ A, b, c, etc. attached to the peaks of the H-NMR chart are those belonging to the hydrogen atoms with the subscripts a, b, c, etc. of the structural formulas described in the chart, ^Thirteen The numbers such as 1, 2, 3 attached to the peaks of the C-NMR chart are assigned to the carbon atoms with the suffixes 1, 2, 3, etc. of the structural formulas shown in the chart. In addition, as a result of elemental analysis of the obtained purified product, 61.91% of carbon (calculated value: 61.95%), 8.70% of hydrogen (calculated value: 8.45%), and 9.03% of nitrogen (calculated) Value; 8.90%).
From the NMR chart and the results of the elemental analysis, it was confirmed that the obtained purified product was 2- (1-aziridinyl) ethyl methacrylate.
Next, 4.66 g (30.1 mmol) of the purified 2- (1-aziridinyl) ethyl methacrylate was mixed with 5.0 ml of tetrahydrofuran and 0.89 g of calcium hydride, and the break seal was stirred together with a stirrer. It was sealed in a welded glass container. This mixture was stirred for 12 hours and further purified by distillation on a high vacuum line. 4.45 g (28.7 mmol) of the purified 2- (1-aziridinyl) ethyl methacrylate was diluted with tetrahydrofuran to prepare a 0.45 mol / L solution. This solution was dispensed into ampoules, sealed, and subjected to anionic polymerization.
[0018]
(3) Anionic polymerization
In the anionic polymerization, diphenylmethyl whose counter cation is a monovalent alkali metal ion is used as an anionic polymerization initiator in 12.84 ml (monomer amount: 5.77 mmol) of a solution of 2- (1-aziridinyl) ethyl methacrylate in tetrahydrofuran. 3.96 mL of potassium tetrahydrofuran solution (dipotassium diphenylmethyl; 0.0939 mmol) and 2.17 mL of diethyl zinc zinc tetrahydrofuran solution (diethyl zinc; 1.60 mmol, 17 molar equivalents of diphenylmethyl potassium) ), And 1 × 10 ^-6 Polymerization was carried out at -78 ° C under a reduced pressure of mmHg for 1 hour to obtain a living polymer. Thereafter, the glass polymerization vessel was opened, and a small amount of methanol was added to stop the polymerization. Then, the obtained polymerization solution was poured into a large amount of n-hexane to precipitate the polymer. The precipitated polymer was separated by filtration and dried. The polymer yield is 99% and the crude polymer solution ¹ When the H-NMR measurement was performed, the signal of the hydrogen atom of the monomer belonging to the subscripts a and b of the structural formula shown in FIG. 1 was almost completely eliminated, and the subscript d of the structural formula shown in FIG. From the ratio of the integral value of the signal of the hydrogen atom of the assigned monomer to the integral value of the signal of the hydrogen atom of the polymer assigned to the subscript c of the structural formula shown in FIG. 3, the conversion of the monomer was 99%.
[0019]
(4) Measurement of number average molecular weight and molecular weight distribution
The polymer obtained by the above method was dissolved in tetrahydrofuran (concentration: 10 mg / ml), and the number average molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC). The molecular weight distribution is the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the GPC method. Table 2 shows the obtained results. The molecular weight distribution was 1.07, and a polymer having a narrow molecular weight distribution could be quantitatively obtained in a short polymerization time.
[0020]
(5) Purification and structural analysis of polymer
The polymer obtained by the above method was dissolved in tetrahydrofuran so as to have a polymer concentration of 7.0% by mass, and this solution was poured into 10-fold volume of n-hexane to reprecipitate and purify the polymer. The precipitated polymer was separated by filtration, dissolved in benzene to a polymer concentration of 15% by mass, and freeze-dried. ¹ H-NMR and ^Thirteen C-NMR measurement was performed. In FIG. ¹ H-NMR measurement results are shown in FIG. ^Thirteen The measurement results of C-NMR are shown. Here, the suffixes a, b, c, etc. and the suffixes 1, 2, 3, etc. are the same as those described with reference to FIGS. ¹ H-NMR, ^Thirteen In the general formula (I), the polymer obtained from the C-NMR chart is represented by R ¹ ~ R ⁴ Is a hydrogen atom, and m is 2, It was confirmed that it is a polymer of methacrylic acid 2- (1-aziridinyl) ethyl ester.
[0021]
Example 2
A living room was prepared in the same manner as in Example 1 except that the monomer synthesized and purified in Example 1 was used, and the amount of the monomer, the amount of the polymerization initiator added, the amount of diethylzinc added and the polymerization time were changed to those shown in Table 1. Polymerization was carried out. Addition of a small amount of methanol to terminate the polymerization ¹ H-NMR and ^Thirteen As a result of measuring the C-NMR, charts similar to those in FIGS. 3 and 4 were shown, and it was confirmed that the obtained living polymer was a living polymer having the same structure as in Example 1. Table 2 shows the yield and conversion of the living polymer.
As in Example 1, the molecular weight distribution was as good as 1.07, and the desired living polymer was obtained quantitatively in a short polymerization time.
[0022]
Example 3
7.03 mL of a tetrahydrofuran solution of the monomer synthesized and purified in Example 1 (2- (1-aziridinyl) ethyl methacrylate; 3.16 mmol), n-butyllithium as an alkyllithium salt as a polymerization initiator 2.81 ml of a heptane solution (sec-butyllithium; 0.0868 mmol), 2.32 ml of a solution of 1,1-diphenylethylene which is 1,1-diarylethylene in tetrahydrofuran (1,1-diphenylethylene; 0.143) Mmol) and 2.69 ml of lithium chloride in tetrahydrofuran (lithium chloride; 0.299 mmol), and the living polymer was polymerized in the same manner as in Example 1 except that the polymerization time was changed to 48 hours. Of the polymer obtained as in Example 1 ¹ H-NMR and ^Thirteen As a result of measuring the C-NMR, charts similar to those in FIGS. 3 and 4 were shown, and it was confirmed that the obtained living polymer was a living polymer having the same structure as in Example 1. Table 2 shows the yield and conversion of the living polymer.
Although it took a long time to obtain a polymer quantitatively at a slightly lower polymerization rate, a living polymer having a narrow molecular weight distribution of 1.04 was obtained in high yield.
[0023]
Comparative Example 1
Anion polymerization was carried out in the same manner as in Example 1 except that the monomer synthesized and purified in Example 1 was used, the amount of the monomer and the amount of the polymerization initiator added were changed to those shown in Table 1, and diethylzinc was not added. Was done. Of the resulting polymer ¹ H-NMR and ^Thirteen As a result of measuring the C-NMR, the same spectrum as in FIGS. 3 and 4 was observed, and it was confirmed that the obtained polymer had the same chemical structure as that of Example 1. Table 2 shows the yield and conversion of the polymer.
Although the polymerization was completed within one hour, the molecular weight distribution of the obtained polymer was as broad as 1.24.
[0024]
Comparative Example 2
Anion polymerization was performed in the same manner as in Example 3 except that the monomer synthesized and purified in Example 1 was used, the amount of the monomer and the amount of the polymerization initiator added were changed to those shown in Table 1, and lithium chloride was not added. Was done. Of the resulting polymer ¹ H-NMR and ^Thirteen As a result of measuring the C-NMR, the same spectrum as in FIGS. 3 and 4 was observed, and it was confirmed that the obtained polymer had the same chemical structure as that of Example 1. Table 2 shows the yield and conversion of the polymer.
Although the polymerization was completed within 1 hour, the molecular weight distribution of the obtained polymer was as broad as 2.19.
[0025]
Comparative Example 3
14.6 mmol of the monomer synthesized and purified in Example 1 and 30 mL of benzene as a solvent were added to a polymerization tube equipped with a three-way cock, and 0.274 mmol of azoisobutyronitrile (AIBN) was added as a polymerization initiator. × 10 ^-3 Radical polymerization was performed at 70 ° C. under a reduced pressure of mmHg. 14 hours after the start of the polymerization, the polymerization solution was frozen with liquid nitrogen to terminate the polymerization. Thereafter, the obtained polymerization solution was poured into a large amount of n-hexane to precipitate the polymer. The precipitated polymer was separated by filtration and dried. The yield was 95% and the conversion of the monomer was 91%.
Next, the dried polymer was redissolved in tetrahydrofuran and poured into a large amount of n-hexane to reprecipitate the polymer. The precipitated polymer is dissolved in benzene and freeze-dried. ¹ H-NMR and ^Thirteen As a result of measuring the C-NMR, the same spectrum as in FIGS. 3 and 4 was observed, and it was confirmed that the obtained polymer had the same chemical structure as that of Example 1. Table 2 shows the yield and conversion of the polymer.
The molecular weight distribution of the obtained polymer was as wide as 3.77.
[0026]
[Table 1]

[0027]
* 1 Ph ₂ CHK; diphenylmethyl potassium
* 2 sec-BuLi; sec-butyllithium
* 3 AIBN: azobisisobutyronitrile
* 4 DPE; 1,1-diphenylethylene
* 5 LiCl; lithium chloride
* 6 Et ₂ Zn; diethyl zinc
[0028]
[Table 2]

[0029]
* 7 Calculated value: Calculated value of molecular weight calculated from terminal functional group of initiator and monomer / initiator molar ratio
* 8 Measured value: between the terminal functional group of the initiator and the functional group contained in the repeating structural unit of the polymer ¹ Actual measured value of molecular weight calculated from area ratio obtained from H-NMR measurement
* 9 Number average molecular weight and molecular weight distribution; measured using N, N-dimethylformamide (lithium iodide-added product, 0.01 mol / L) as the mobile phase at a column temperature of 40 ° C and a liquid sending rate of 1.0 mL / min. And a value converted using the molecular weight of standard polystyrene (GPC device; high-speed GPC device “HLC-8120GPC” (manufactured by Tosoh Corporation); high-speed column; TSK guard column H _XL -H, TSK gel GMH _XL , TSK gel GMH _XL , And TSK gel G2000H _XL (All manufactured by Tosoh Corporation) used in this order, detectors: differential refractometer and ultraviolet-visible detector (wavelength: 254 nm)
* 10 The measured molecular weight of the radical polymer is measured according to * 9 above.
[0030]
Example 4
(1) Purification of methyl methacrylate
25.0 g (0.25 mol) of commercially available methyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) was washed with 50 ml of 5.0 mass% sodium hydroxide aqueous solution and 50 ml of deionized water to remove the polymerization inhibitor. After that, 3.6 g of anhydrous magnesium sulfate was added and the mixture was dehydrated for 12 hours. After filtering off the dehydrating agent, 2.5 g of calcium hydride was added and dried for 24 hours. Then, in the presence of calcium hydride, vacuum distillation was performed at 49.1 to 49.5 ° C. and 113 mmHg to obtain 23.3 g (0.23 mol) of dehydrated methyl methacrylate.
7.36 g (73.6 mmol) of dehydrated methyl methacrylate, 1.06 g of calcium hydride and 11.1 ml of n-heptane were sealed in a 50 ml round bottom flask equipped with a break seal. After stirring this mixed solution for 12 hours, it was distilled and purified on a high vacuum line. Further, the residue was purified by distillation in a high vacuum line in the presence of 1.41 mmol of tri (n-octyl) aluminum to obtain 6.57 g (65.7 mmol) of methyl methacrylate. The obtained methyl methacrylate was diluted with tetrahydrofuran to prepare a 0.69 mol / liter solution. This solution was dispensed into ampoules provided with break seals, sealed and subjected to anionic polymerization.
[0031]
(2) Block copolymerization
5.59 ml of a diphenylmethyl potassium tetrahydrofuran solution (diphenylmethyl potassium; 0.130 mmol) as an anionic polymerization initiator was transferred to the polymerization vessel sealed under a high vacuum via a break seal, and cooled to -78 ° C. Thereafter, the temperature was maintained until the polymerization was stopped.
Next, 4.27 ml of a diethyl zinc solution in tetrahydrofuran (diethyl zinc; 1.68 mmol) was added, and the mixture was reacted for 20 minutes. 12.47 ml of a tetrahydrofuran solution of-(1-aziridinyl) ethyl (2- (1-aziridinyl) ethyl methacrylate; 5.76 mmol) was added, polymerization was carried out for 20 minutes with sufficient stirring, and methacrylic acid 2- ( A living polymer of 1-aziridinyl) ethyl was obtained.
Subsequently, 12.03 ml of a purified solution of methyl methacrylate in tetrahydrofuran (methyl methacrylate; 4.18 mmol) was added, polymerization was carried out for 15 minutes with sufficient stirring, and then 5.80 ml of a solution of methanol in tetrahydrofuran ( (Methanol; 18.4 mmol) was added to terminate the polymerization.
After concentrating this polymerization solution using an evaporator, it was poured into a large amount of n-hexane to precipitate a polymer (block copolymer), which was separated by filtration and dried. The yield of the polymer was 96%. In addition, unpurified polymerization solution ¹ From the results of the H-NMR measurement, it was confirmed that both the conversion rates of 2- (1-aziridinyl) ethyl methacrylate and methyl methacrylate were 99%. The calculated average molecular weight of the obtained polymer was 10,000, and the measured value was 12,000. The molecular weight distribution was 1.05 as shown in FIG.
[0032]
(3) Polymer purification and structural analysis
The polymer obtained by the above method was dissolved in tetrahydrofuran so as to have a polymer concentration of 7.0% by mass, and this solution was poured into 10-fold volume of n-hexane to reprecipitate and purify the polymer. The precipitated polymer was separated by filtration, dissolved in benzene to a polymer concentration of 15% by mass, and freeze-dried. ¹ 1 H-NMR measurement was performed. In FIG. ¹ The measurement result of 1 H-NMR is shown. Here, the subscripts a, b, c, etc. are the same as those described in FIG. ¹ From the H-NMR chart, it was confirmed that the obtained polymer was a block polymer of 2- (1-aziridinyl) ethyl methacrylate and methyl methacrylate.
[0033]
【The invention's effect】
According to the present invention, a living polymer of a methacrylic acid (alkyl-substituted) aziridinylalkyl ester having a narrow molecular weight distribution, which is a polymer of an alkyl methacrylate having an alkyleneimine group in a side chain, can be obtained in high yield. it can.
Since the living polymer has a high reactivity of the alkyleneimine group, a pressure-sensitive adhesive, an adhesive, a crosslinking agent for paint, a resist material, a coating agent, a crosslinking agent in the field of film formation, a main polymer, a base resin, and the like. Can be expected to be widely applied as raw materials
[Brief description of the drawings]
FIG. 1 shows the monomer of Example 1 ¹ It is an H-NMR chart.
FIG. 2 of the monomer of Example 1 ^Thirteen It is a C-NMR chart.
FIG. 3 shows a sample obtained by terminating the living polymer of Example 1 with methanol. ¹ It is an H-NMR chart.
FIG. 4 shows a sample obtained by terminating the living polymer of Example 1 with methanol. ^Thirteen It is a C-NMR chart.
FIG. 5 is a GPC curve of the copolymer of Example 4.
FIG. 6 is a diagram showing a copolymer obtained by terminating polymerization of the copolymer of Example 4 with methanol. ¹ It is an H-NMR chart.

Claims (6)

It has a repeating unit represented by the following general formula (I), has a number average molecular weight (Mn) of 1,000 to 100,000, and has a molecular weight distribution (Mw / Mn, Mw is a weight average molecular weight) of 1 A living polymer of methacrylic acid (alkyl-substituted) aziridinylalkyl ester having a molecular weight of 20 or less.

(R ^{1 to} R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. M is an integer of 1 to 8.) The living polymer of aziridinyl methacrylate alkyl ester according to claim 1, wherein R ^{1 to} R ^{4 of the} living polymer are hydrogen atoms, and m is 2. A block copolymer containing the repeating unit represented by the general formula (I) as a segment. An methacrylic acid (alkyl-substituted) aziridinylalkyl ester represented by the following general formula (II) is anionized using an anion polymerization initiator whose counter cation is a monovalent alkali metal ion and an initiator system containing dialkylzinc. The method for producing a living polymer according to claim 1, wherein the polymerization is carried out.

(R ^{1 to} R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. M is an integer of 1 to 8.) The method for producing a living polymer according to claim 4, wherein the alkali metal ion of the polymerization initiator is a potassium ion. It is characterized in that the methacrylic acid (alkyl-substituted) aziridinyl alkyl ester represented by the general formula (II) is anion-polymerized using an alkyl lithium salt and an initiator system containing 1,1-diarylethylene and lithium chloride. A method for producing a living polymer.

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