JP4549508B2 - Polymerization method of methacrylic acid ester or acrylic acid ester - Google Patents

Description

【０１０６】
上記表１中、「有機アルミニウム化合物」及び「添加剤」の欄における記号は以下の化合物を意味する。
【０１０７】
iB_２Al(BHT)：ジイソブチル（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム
iBAl(BHT)_２：イソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム
Et_３Al：トリエチルアルミニウム
iB_３Al：トリイソブチルアルミニウム
DME：１，２−ジメトキシエタン
【０１０８】
上記表１に示された実施例２〜５の結果から、メタクリル酸エステルを、アニオン重合開始剤化合物を用いて有機アルミニウム化合物の存在下に重合するに際し、該アニオン重合開始剤化合物としてポリスチリルリチウムのような有機アルカリ金属化合物と共役ジエン化合物との付加反応生成物を使用し、かつ該有機アルミニウム化合物として上記の特定の有機アルミニウム化合物（Ｉ）を使用した場合には、高い開始効率（ブロック効率）を達成できることが分かる。これに対し、表１に記載された比較例３〜７の結果から、該有機アルミニウム化合物として一般的な有機アルミニウム化合物であるトリアルキルアルミニウムを使用した場合（比較例３及び４）には開始効率（ブロック効率）が低くなり、また、アニオン重合開始剤化合物としてポリスチリルリチウムのような有機アルカリ金属化合物をそのままの形態又は共役ジエン化合物以外の不飽和化合物との付加反応生成物の形態で使用した場合（比較例５〜７）には、重合率が極めて低くなるか、又は開始効率（ブロック効率）が低くなることが分かる。
【０１０９】
実施例６（スチレン−アクリル酸ｎ−ブチルブロック共重合体の合成例）
本実施例は、スチレンのアニオン重合によるポリスチリルリチウム（有機アルカリ金属化合物）の調製工程、ブタジエンの付加反応による重合開始剤化合物の調製工程、及びイソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウム（有機アルミニウム化合物）の存在下におけるアクリル酸ｎ−ブチルの重合工程からなるスチレン−アクリル酸ｎ−ブチルブロック共重合体の製造例である。なお、ブロック共重合におけるブロック効率（アクリル酸ｎ−ブチルの重合における開始効率）は、ブロック共重合体のＧＰＣ測定によって求められたポリスチレン換算数平均分子量と、使用量及び収率に基づいて算出されたブロック共重合体の分子量との比から求めた。
【０１１０】
イソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液及び１，２−ジメトキシエタンを混合して調製した溶液の添加温度を０℃から−３０℃に変更し、かつメタクリル酸メチル２．２５ｇを０℃で添加し０℃で１時間重合させた代わりに、アクリル酸ｎ−ブチル２．２５ｇを−３０℃で添加し−３０℃で５分間重合させた以外は実施例５と同様にして、スチレンのアニオン重合によるポリスチリルリチウムの調製、ブタジエンの付加反応による重合開始剤化合物の調製、及び有機アルミニウム化合物の存在下におけるアクリル酸ｎ−ブチルの重合を順次行った。
得られた重合開始剤化合物についてのＧＰＣ（ポリスチレン換算）分析の結果、Ｍｎは５０００であり、Ｍｗ／Ｍｎは１．０４であることが判明した。
アクリル酸ｎ−ブチルの重合工程後、再沈により重合体を得た。得られた重合体の収率はほぼ１００％であった。また、ＧＰＣ−ＵＶ（２５４ｎｍ）測定（ポリスチレン換算）の結果、該重合体は、Ｍｎ＝２１５００、Ｍｗ／Ｍｎ＝１．０９のブロック共重合体と、重合開始剤化合物由来の重合体（末端にブタジエン断片を有するポリスチレン）との混合物であり、前者：後者の重量比は９６：４であることが判明した。
重合開始剤重合体の分子量、ブロック共重合体の分子量及び収率に基づき、ブロック効率は９１％と見積もられた。
使用した化学物質、採用した重合条件及び得られた結果を、下記表２に示す。
【０１１１】
実施例７（スチレン−アクリル酸ｎ−ブチルブロック共重合体の合成例）
０．８０ｍｍｏｌのイソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液１．０ｍｌ及び１，２−ジメトキシエタン０．２２ｇを混合して調製した溶液を添加する代わりに、０．４０ｍｍｏｌのイソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液０．５０ｍｌのみを添加し、アクリル酸ｎ−ブチル単独を添加する代わりに、それと同重量のアクリル酸ｎ−ブチルを０．４０ｍｍｏｌのイソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液０．５０ｍｌと混合して調製した溶液を添加し、かつアクリル酸ｎ−ブチルの重合時間を５分間から３０分間に変更した以外は実施例６と同様にして、スチレンのアニオン重合によるポリスチリルリチウムの調製、ブタジエンの付加反応による重合開始剤化合物の調製、及び有機アルミニウム化合物の存在下におけるアクリル酸ｎ−ブチルの重合を順次行った。
得られた重合開始剤化合物についてのＧＰＣ（ポリスチレン換算）分析の結果、Ｍｎは５１００であり、Ｍｗ／Ｍｎは１．０２であることが判明した。
アクリル酸ｎ−ブチルの重合工程後、再沈により重合体を得た。得られた重合体の収率はほぼ１００％であった。また、ＧＰＣ−ＵＶ（２５４ｎｍ）測定（ポリスチレン換算）の結果、該重合体は、Ｍｎ＝２４０００、Ｍｗ／Ｍｎ＝１．１２のブロック共重合体と、重合開始剤化合物由来の重合体（末端にブタジエン断片を有するポリスチレン）との混合物であり、前者：後者の重量比は９３：７であることが判明した。
重合開始剤重合体の分子量、ブロック共重合体の分子量及び収率に基づき、ブロック効率は８１％と見積もられた。
使用した化学物質、採用した重合条件及び得られた結果を、下記表２に示す。
【０１１２】
比較例８
イソブチルビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムの代わりにそれと同モル数のトリイソブチルアルミニウムを使用し、かつアクリル酸ｎ−ブチルの重合時間を５分間から６時間に変更した以外は実施例６と同様にして、スチレンのアニオン重合によるポリスチリルリチウムの調製、ブタジエンの付加反応による重合開始剤化合物の調製、及び有機アルミニウム化合物の存在下におけるアクリル酸ｎ−ブチルの重合を順次行った。
得られた重合開始剤化合物についてのＧＰＣ（ポリスチレン換算）分析の結果、Ｍｎは５８００であり、Ｍｗ／Ｍｎは１．０４であることが判明した。
アクリル酸ｎ−ブチルの重合工程後、再沈により重合体を得た。得られた重合体についての^１Ｈ−ＮＭＲ分析の結果、アクリル酸ｎ−ブチルは全く重合していないことが判明した。また、ＧＰＣ−ＵＶ（２５４ｎｍ）測定（ポリスチレン換算）の結果、該重合体は重合開始剤化合物由来の重合体（末端にブタジエン断片を有するポリスチレン）であることが判明した。
使用した化学物質、採用した重合条件及び得られた結果を、下記表２に示す。
【０１１３】
【表２】

【０１１４】
上記表２中、「有機アルミニウム化合物」及び「添加剤」の欄における記号は以下の意味を有する。
iBAl(BHT)_２：イソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム
iB_３Al：トリイソブチルアルミニウム
DME：１，２−ジメトキシエタン
ａ）：アクリル酸ｎ−ブチルとの混合物の形態で添加
【０１１５】
上記表２に示された結果から、アクリル酸エステルを、有機アルカリ金属化合物と共役ジエン化合物との付加反応生成物からなる重合開始剤化合物を用いて有機アルミニウム化合物の存在下に重合するに際し、該有機アルミニウム化合物として、上記の特定の有機アルミニウム化合物（Ｉ）を使用した場合（実施例６及び７）には高い開始効率（ブロック効率）を達成できるが、一般的な有機アルミニウム化合物であるトリアルキルアルミニウムを使用した場合（比較例８）には重合反応が進行しないことが分かる。
【０１１６】
実施例８（メタクリル酸メチル重合体の合成例）
本実施例は、ｓｅｃ−ブチルリチウム（有機アルカリ金属化合物）に対する少割合のブタジエンの付加反応によるオリゴブタジエニルリチウム（重合開始剤化合物）の調製工程、及びジイソブチル（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウム（有機アルミニウム化合物）の存在下におけるメタクリル酸メチルの重合工程からなるメタクリル酸メチル重合体の製造例である。なお、メタクリル酸メチルの重合体における開始効率は、メタクリル酸メチル重合体のＧＰＣ測定によって求められたポリスチレン換算数平均分子量と、使用量及び収率に基づいて算出されたメタクリル酸メチル重合体の分子量との比から求めた。
【０１１７】
（１）５０ｍｌの三方コック付きシュレンク管にマグネチックスターラーチップを入れ、容器内を窒素置換した。これに、１．２ｇのブタジエンを含有するシクロヘキサン溶液１８．５ｍｌを加え、０℃に冷却した。この溶液に、濃度１．３Ｍのｓｅｃ−ブチルリチウムのシクロヘキサン溶液１．６ｍｌを加え、０℃で２４時間、撹拌下に反応を行った。
得られた反応混合液についてのＧＰＣ測定の結果、ポリスチレン換算数平均分子量（Ｍｎ）が１２００であり、分子量分布（Ｍｗ／Ｍｎ）が１．１８であるオリゴブタジエニルリチウムが生成していることが判った。
【０１１８】
（２）５０ｍｌの三方コック付きシュレンク管にマグネチックスターラーチップを入れ、容器内を窒素置換した。これに、トルエン１５ｍｌ及び上記（１）で調製した濃度０．１Ｍのオリゴブタジエニルリチウムのシクロヘキサン溶液のうちの１．５ｍｌを加えた。この溶液を−３０℃に冷却し、０．８０ｍｍｏｌのジイソブチル（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液１．０ｍｌを加え、１０分間撹拌した。
次いで、得られた溶液を激しく撹拌しながら、これにメタクリル酸メチル１．５０ｇを加えた。−３０℃で２時間、攪拌下に重合を行った後、メタノールを約０．０５ｍｌ加えることにより、重合を停止させた。
得られた反応混合液を３００ｍｌのメタノールに再沈させることにより、重合体を取得した。得られた重合体の収率はほぼ１００％であった。ＧＰＣ測定（ポリスチレン換算）の結果、該重合体についてはＭｎ＝１１９００及びＭｗ／Ｍｎ＝１．０７であることが判明した。
これらのことから、メタクリル酸メチルの重合における開始効率は９３％であることが判った。
使用した化学物質、採用した重合条件及び得られた結果を、下記表３に示す。
【０１１９】
比較例９
５０ｍｌの三方コック付きシュレンク管にマグネチックスターラーチップを入れ、容器内を窒素置換した。これにトルエン１５ｍｌを加え、−３０℃に冷却した後、濃度１．６Ｍのｔｅｒｔ−ブチルリチウムのシクロヘキサン溶液を０．９５ｍｌ加えた。この溶液を−３０℃に保ち、０．８０ｍｍｏｌのジイソブチル（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノキシ）アルミニウムを含有するトルエン溶液１．０ｍｌを加え、１０分間撹拌した。
次いで、得られた溶液を激しく撹拌しながら、これに、メタクリル酸メチル１．５０ｇを加えた。−３０℃で２時間、攪拌下に重合を行った後、メタノールを約０．０５ｍｌ加えることにより、重合を停止させた。
得られた反応混合液を３００ｍｌのメタノールに再沈させることにより、重合体を取得した。得られた重合体の収率はほぼ１００％であった。ＧＰＣ測定（ポリスチレン換算）の結果、該重合体についてはＭｎ＝１３０００及びＭｗ／Ｍｎ＝１．１１であることが判明した。
これらのことから、メタクリル酸メチルの重合における開始効率は７７％であることが判った。
使用した化学物質、採用した重合条件及び得られた結果を、下記表３に示す。
【０１２０】
比較例１０
濃度１．６Ｍのｔｅｒｔ−ブチルリチウムのシクロヘキサン溶液０．９５ｍｌの代わりに濃度１．３Ｍのｓｅｃ−ブチルリチウムのシクロヘキサン溶液１．１５ｍｌを使用し、かつメタクリル酸メチルの重合時間を２時間から６時間に延長した以外は比較例９と同様にして、有機アルミニウム化合物の存在下におけるメタクリル酸メチルの重合を試行した。
しかしながら、メタクリル酸メチルは重合していないことが判明した。
使用した化学物質、採用した重合条件及び得られた結果を、下記表３に示す。
【０１２１】
比較例１１
濃度１．６Ｍのｔｅｒｔ−ブチルリチウムのシクロヘキサン溶液０．９５ｍｌの代わりに濃度１．５Ｍのｎ−ブチルリチウムのシクロヘキサン溶液１．０ｍｌを使用し、かつメタクリル酸メチルの重合時間を２時間から６時間に延長した以外は比較例９と同様にして、有機アルミニウム化合物の存在下におけるメタクリル酸メチルの重合を試行した。
しかしながら、メタクリル酸メチルは重合していないことが判明した。
使用した化学物質、採用した重合条件及び得られた結果を、下記表３に示す。
【０１２２】
【表３】

【０１２３】
上記表３中、「有機アルミニウム化合物」の欄における記号は以下の化合物を意味する。
【０１２４】
iB_２Al(BHT)：ジイソブチル（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム
【０１２５】
上記表３に示された実施例８の結果から、メタクリル酸エステルを、アニオン重合開始剤化合物を用いて、アルミニウム原子が有する３個の結合手のうちの１個が酸素原子を介して芳香環と結合している化学構造を有する有機アルミニウム化合物の存在下に重合するに際し、該アニオン重合開始剤化合物として、低分子量アルキルリチウムのような有機アルカリ金属化合物と共役ジエン化合物との付加反応生成物を使用した場合には、高い開始効率を達成できることが分かる。これに対し、表３に記載された比較例９〜１１の結果から、アニオン重合開始剤化合物として、低分子量アルキルリチウムのような一般的な重合開始剤化合物をそのまま使用した場合には、重合率が極めて低いか、又は開始効率が低いことが分かる。
【０１２６】
実施例９（ブタジエン−メタクリル酸メチルジブロック共重合体の合成例）
本実施例は、ｓｅｃ−ブチルリチウム（有機アルカリ金属化合物）に対し多量のブタジエンの付加反応（重合）によるポリブタジエンのリビングアニオン（ポリブタジエニルリチウム；重合開始剤化合物）の調製工程、及びイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム（有機アルミニウム化合物）の存在下におけるメタクリル酸メチルの重合工程からなるブタジエン−メタクリル酸メチルジブロック共重合体の製造例である。
（１）１リットルのオートクレーブ装置の内部を窒素置換し、これに、トルエン５２０ｇと濃度１．３Ｍのｓｅｃ−ブチルリチウムのシクロヘキサン溶液２．５ｍｌを加えた。得られた溶液に１８℃でブタジエン６５ｇを加え、５時間重合させることにより、ポリブタジエンのリビングアニオンを得た。
得られた反応混合液からサンプルを採取しＧＰＣで測定した結果、生成したポリブタジエンについて、ポリスチレン換算数平均分子量（Ｍｎ）は２９，４００であり、分子量分布（Ｍｗ／Ｍｎ）は１．０１であることが判った。
（２）上記（１）で得られた反応混合液を−３℃まで冷却し、これに、濃度０．８Ｍのイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウムのトルエン溶液２０ｍｌと１，２−ジメトキシエタン６ｍｌとから調製した混合液を加え、１０分間撹拌した。さらに、この溶液に、メタクリル酸メチル６５ｇと濃度０．８Ｍのイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウムのトルエン溶液３ｍｌから調製した混合液を加え、０℃にて２時間重合した。
得られた反応混合液からサンプルを採取しＧＰＣで測定した結果、生成した重合体について、ポリスチレン換算数平均分子量（Ｍｎ）は４９，３００であり、分子量分布（Ｍｗ／Ｍｎ）は１．０３であることが判明した。また、上記（１）で得られたポリブタジエン（ホモポリマー）に由来するピークは観測されず、生成した重合体はブタジエン−メタクリル酸メチルジブロック共重合体（ＰＢｄ−ｂ−ＰＭＭＡ）のみであることが判った。さらに、サンプルの^１Ｈ−ＭＮＲ分析の結果、得られた重合体におけるポリブタジエンブロック／ポリメタクリル酸メチルブロックの重量比は４７／５３であり、ポリブタジエンブロックにおける１，４結合／１，２結合の比（モル比）は１０／９０であることが判明した。
【０１２７】
参考例１
本参考例は、実施例９で得られたブロック共重合体を水素添加することにより、ポリブタジエンブロックを実質的なエチレン−ブチレン共重合体ブロックに変換させたブロック共重合体の製造例である。
ニッケル／アルミニウム系水素添加用触媒（ニッケル含有量：１ミリモル；アルミニウム含有量：３ミリモル）と反応させ、これを、実施例９で最終的に得られた反応混合液に加えた。得られた混合液を水素加圧（１ＭＰａ）雰囲気下に撹拌しながら８０℃まで昇温し、この温度で３時間反応させた。この間、水素を供給することにより、水素圧を１ＭＰａを保持した。
得られた反応混合液の^１Ｈ−ＭＮＲ分析の結果、生成した重合体においては、ポリブタジエンブロックの二重結合の９８％が消失しており、水添ポリブタジエンブロックとポリメタクリル酸メチルブロックを有するジブロック共重合体（水添ＰＢｄ−ｂ−ＰＭＭＡ）が得られたことが判明した。
【０１２８】
実施例１０（イソプレン−アクリル酸ｎ−ブチルジブロック共重合体の合成例）本実施例は、ｓｅｃ−ブチルリチウム（有機アルカリ金属化合物）に対し多量のイソプレンを付加反応（重合）させたポリイソプレンのリビングアニオン（ポリイソプレニルリチウム；重合開始剤化合物）の調製工程、及びイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウム（有機アルミニウム化合物）の存在下におけるアクリル酸ｎ−ブチルの重合工程からなるイソプレン−アクリル酸ｎ−ブチルジブロック共重合体の製造例である。
（１）１リットルのオートクレーブ装置の内部を窒素置換し、これに、トルエン４４０ｇと濃度１．３Ｍのｓｅｃ−ブチルリチウムのシクロヘキサン溶液２．８ｍｌを加えた。得られた溶液に２３℃でイソプレン５５ｇを加え、４時間重合させることにより、ポリイソプレンのリビングアニオンを得た。
得られた反応混合液からサンプルを採取しＧＰＣで測定した結果、生成したポリイソプレンについて、ポリスチレン換算数平均分子量（Ｍｎ）は１１，０００であり、分子量分布（Ｍｗ／Ｍｎ）は１．０２であることが判った。
（２）上記（１）で得られた反応混合液を−３１℃まで冷却し、これに、濃度０．８Ｍのイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウムのトルエン溶液を４０ｍｌと１，２−ジメトキシエタン７ｍｌとから調製した混合液を加え、１０分間撹拌した。さらに、この溶液に、アクリル酸ｎ−ブチル５５ｇと濃度０．８Ｍのイソブチルビス（２，６−ジ−ｔ−ブチル−４−メチルフェノキシ）アルミニウムのトルエン溶液５ｍｌから調製した混合液を加え、−２７℃にて２時間重合した。
得られた反応混合液からサンプリングを採取しＧＰＣで測定した結果、生成した重合体について、ポリスチレン換算数平均分子量（Ｍｎ）は３７，８００であり、分子量分布（Ｍｗ／Ｍｎ）は１．０３であることが判明した。また、上記（１）で得られたポリイソプレン（ホモポリマー）に由来するピークは観測されず、生成した重合体はイソプレン−アクリル酸ｎ−ブチルジブロック共重合体（ＰＩｐ−ｂ−ＰｎＢＡ）のみであることが判明した。さらに、サンプルの^１Ｈ−ＭＮＲ分析の結果、得られた重合体におけるポリイソプレンブロック／ポリアクリル酸ｎ−ブチルブロックの重量比は４９／５１であり、ポリイソプレンブロックにおける１，４結合／３，４結合の比（モル比）は７／９３であることが判明した。
得られたイソプレン−アクリル酸ｎ−ブチルジブロック共重合体及び上記（１）で得られたポリイソプレンについて、ＧＰＣチャートを図１に重ねて示す。なお、図１中、曲線Ａ及び曲線Ｂは、それぞれイソプレン−アクリル酸ｎ−ブチルジブロック共重合体及びポリイソプレンを示す。
【０１２９】
上記実施例９及び１０より、本発明の製造方法によれば、ジエン重合体ブロックと（メタ）アクリル酸エステル重合体ブロックとを有するブロック共重合体を、狭い分子量分布で、かつ極めて高いブロック効率で製造し得ることが判る。
【０１３０】
【発明の効果】
本発明によれば、メタクリル酸メチル、メタクリル酸ｔｅｒｔ−ブチル、アクリル酸ｎ−ブチルなどの幅広い（メタ）アクリル酸エステルについて、ｓｅｃ−ブチルリチウムのような利便性が比較的良好な有機アルカリ金属化合物を使用し、炭化水素系溶媒のような回収・再利用が容易な溶媒中、例えば−３０℃〜１５℃のような緩和された冷却条件下において、高い開始効率及び高いリビング性でアニオン重合させることが可能となる。したがって、本発明によれば、ブロック共重合体等の（メタ）アクリル酸エステル系重合体を工業的に有利に製造することができる。
【図面の簡単な説明】
【図１】図１は、本発明に従う実施例１０において最終的に得られたイソプレン−アクリル酸ｎ−ブチルジブロック共重合体のＧＰＣチャート（Ａ）及び該ジブロック共重合体を製造するための第一工程で調製したポリイソプレンのＧＰＣチャート（Ｂ）である。横軸は流出時間を表す。[0001]
BACKGROUND OF THE INVENTION
The present invention is a polymerization excellent in reaction results such as initiation efficiency, comprising anionic polymerization of methacrylic acid ester or acrylic acid ester in the presence of a specific organoaluminum compound using a specific polymerization initiator compound. Regarding the method. Moreover, this invention relates to the manufacturing method of polymers, such as a block copolymer, which employ | adopted this polymerization method.
[0002]
[Prior art]
In anionic polymerization, it is important to increase the starting efficiency in addition to realizing high living properties. High initiation efficiency is not only important in increasing the utilization efficiency of the polymerization initiator compound, but is particularly important in the synthesis of block copolymers. For example, a living polymer is synthesized by polymerization of a certain monomer (hereinafter referred to as “first monomer”), and then the other polymer is used by using the living polymer as a polymerization initiator compound. (Hereinafter referred to as “second monomer”), which is a block copolymer having a polymer block composed of a first monomer and a polymer block composed of a second monomer. A method for synthesizing a polymer is assumed, but if the starting efficiency of the living polymer (in this case, the block efficiency) is low, what is actually obtained consists of a block copolymer and a first monomer. It becomes a mixture with a polymer. Impurities formed by such interruption of polymerization often significantly reduce the performance of the block copolymer. For example, it is known that a hard block-soft block-hard block type triblock copolymer has a function as a thermoplastic elastomer. In this type of triblock copolymer, a hard block single polymer is used. When a hard block-soft block type diblock copolymer is mixed, mechanical properties such as tensile strength are lowered. In addition, the block copolymer may be used as a compatibilizer between different resins. However, if a homopolymer is mixed in the block copolymer to be used, the function as the compatibilizer is reduced. In the obtained resin composition, the advantages inherent to each resin are not sufficiently exhibited.
[0003]
With respect to a method for increasing the initiation efficiency in anionic polymerization of methacrylic acid ester or acrylic acid ester, for example, an organic alkali metal compound such as alkyllithium such as butyllithium or a lithiated polymer such as polystyryllithium is used as 1,1 -A compound having a diphenylmethylene anion structure or a phenylmethylene anion structure at the terminal site is prepared by addition reaction with diphenylethylene or α-methylstyrene, and the methacrylate is converted into tetrahydrofuran using the compound as a polymerization initiator compound. A method comprising anionic polymerization at a low temperature of −60 ° C. or less in a solvent composed of a mixture of toluene and toluene alone is known (Macromolecules, Vol. 23, pp. 2618-2622 (1990)). . The polar solvent such as tetrahydrofuran used in the method is not suitable for industrial use because it is easily mixed into the wastewater during the water washing treatment after polymerization and is not easily separated and purified from the wastewater. Therefore, in order to industrially perform anionic polymerization in a methacrylic acid ester or acrylic acid ester solution, it is desirable to use a nonpolar solvent such as a hydrocarbon solvent as a solvent.
[0004]
As a method for enabling anionic polymerization of methacrylic acid ester or acrylic acid ester in a hydrocarbon solvent, it has been proposed that an organoaluminum compound is present in the polymerization system. In this case, the organoaluminum compound is considered to have an action of reducing and stabilizing the nucleophilicity of the growth terminal by coordinating as a Lewis acid to the growth terminal of the polymerization initiator compound or the living polymer in the middle of the polymerization. Yes. Examples of reports of such polymerization methods include the following.
[0005]
(1) Anionic polymerization of methacrylic acid ester using tert-butyllithium is carried out at −78 ° C. in toluene in the presence of an organoaluminum compound such as trialkylaluminum and dialkyl (diphenylamino) aluminum. A methacrylate polymer having a narrow distribution was obtained (Japanese Patent Publication No. 7-57766).
[0006]
(2) Anionic polymerization of methacrylic acid ester using an organolithium compound such as tert-butyllithium is carried out by using a specific organoaluminum compound having one or more bulky groups in a hydrocarbon solvent (eg, triisobutylaluminum, diisobutyl). In the presence of (2,6-di-tert-butyl-4-methylphenoxy) aluminum, etc.) at a temperature of about −10 ° C. which is a relatively relaxed cooling condition (Japanese Patent Laid-Open No. 5-5009) ).
[0007]
(3) Anionic polymerization of methacrylic acid ester or acrylic acid ester using tert-butyllithium is carried out by using methylbis (2,6-di-tert-butylphenoxy) aluminum or ethylbis (2,6-di-tert- (Butylphenoxy) A homopolymer or a block copolymer having a narrow molecular weight distribution was obtained by performing at a temperature of −60 ° C. or −70 ° C. in the presence of aluminum (Polymer Preprints, Japan), 46, No. 7, pages 1081-182 (1997) and 47, No. 2, page 179 (1998)).
[0008]
(4) An organolithium compound such as tert-butyllithium, sec-butyllithium, ethyl α-lithioisobutyrate, 1,1-diphenylhexyllithium, or the like is converted to methylbis (2,6-di-tert-butylphenoxy) aluminum, ethylbis (2 , 6-di-tert-butylphenoxy) aluminum, organic aluminum compounds such as tris (2,6-di-tert-butylphenoxy) aluminum and the like, followed by contacting with methyl methacrylate, An initiation efficiency of 0.05 to 0.63 was achieved by anionic polymerization at a temperature around room temperature in a nonpolar organic solvent such as toluene (Japanese Patent Laid-Open No. 7-330819).
[0009]
(5) Anionic polymerization of methacrylic acid ester or acrylic acid ester using an organic lithium compound such as ethyl α-lithioisobutyrate or tert-butyl lithium, and an organoaluminum compound such as trialkylaluminum in a hydrocarbon solvent such as toluene. And a polymer having a narrow molecular weight distribution was obtained at a temperature of about −80 ° C. to 0 ° C. in the presence of an ester compound, an ether compound or an organic quaternary salt (Macromolecules, Vol. 31, 573 to 577). (1998) and International Application WO 98/23651).
[0010]
(6) Polybutadienyl lithium is prepared by addition reaction of an organolithium compound such as n-butyllithium with butadiene, and the polybutadienyl lithium is tert-methacrylic acid in the presence of trialkylaluminum such as triethylaluminum. By reacting with -butyl at 50 ° C., a block copolymer was obtained (Japanese Patent Laid-Open No. 7-70264).
[0011]
[Problems to be solved by the invention]
According to each of the above methods (1) to (6), anionic polymerization of a methacrylic acid ester or an acrylic acid ester in a hydrocarbon-based solvent is possible. There is a point that should be further improved.
[0012]
In the specific polymerization examples in the above (1) to (3), the polymerization initiator compound used for the polymerization of methacrylic acid ester or acrylic acid ester is limited to tert-butyllithium. In these polymerization methods, the use of tert-butyllithium is presumed to be desirable in order to achieve good polymerization results. However, tert-butyllithium has a strong self-ignition property, and is assumed to be industrially used. However, there are problems in its safety and handling properties such as transportation and storage.
[0013]
In the methods (1) and (3) above, the polymerization temperature employed in the specific polymerization examples among them is a very low temperature such as about -80 to -60 ° C. In these polymerization methods, it is presumed that it is desirable to employ such extremely low temperatures in order to achieve good polymerization results. However, since a large amount of utility is required for cooling, it is industrially necessary. It is disadvantageous.
[0014]
In the method of (4) above, the initiation efficiency in the specific polymerization example of methyl methacrylate is almost always the case even in the case of using tert-butyllithium as a polymerization initiator compound, which provides relatively good polymerization results. Initiation efficiency is still inadequate, such as 0.17 in an example using sec-butyllithium, which is a polymerization initiator compound that is 0.5 or less and handleability is relatively good.
[0015]
The polymerization initiator compound used in the specific polymerization example in the above (5) is limited to tert-butyllithium and ethyl α-lithioisobutyrate. Although it is estimated that the use of these polymerization initiator compounds is desirable in order to achieve good polymerization results, tert-butyllithium has problems in industrial use in terms of safety and handleability as described above. It is. In addition, ethyl α-lithioisobutyrate is not suitable for industrial use because of the complicated synthesis operation for producing it and subsequent purification operation.
[0016]
The inventors tried to reproduce the method (6) experimentally, but did not obtain a predetermined result. That is, based on the specific production example described in (6) above, a predetermined polybutadienyllithium is prepared, and then tert-butyl methacrylate is added to the polybutadienyllithium with triethylaluminum. In the present polymerization system, the reaction was carried out at a temperature of 50 ° C., but in this polymerization system, the initiation efficiency of the polybutadienyl lithium was low, and the final product was a mixture of a block copolymer and polybutadiene. It was. Therefore, the method (6) has a problem when employed in industrial production where high reproducibility is required.
[0017]
Furthermore, as a result of experimental studies by the present inventors on the methods (1) to (6) above, primary alcohols such as methyl methacrylate and n-butyl acrylate, methacrylic acid or acrylic acid are often used. In the case of the ester, even if the polymerization does not proceed, or even if the polymerization reaction proceeds, the reaction such as initiation efficiency, living property, etc., compared with the ester of tertiary alcohol such as tert-butyl methacrylate and methacrylic acid. It was found that the results decreased.
[0018]
In order to make anionic polymerization of methacrylic acid ester or acrylic acid ester suitable for industrial implementation, living property at the time of polymerization is high, start efficiency (block efficiency in the case of block copolymerization) is high, It is important that hydrocarbon solvents can be used as the solvent for polymerization, that the range of usable polymerization initiator compounds or precursor compounds thereof (organic alkali metal compounds) is wide, and that the cooling conditions during polymerization can be relaxed. is there. Furthermore, it is desired as an industrial process from the viewpoint of high versatility that an ester of a primary alcohol and methacrylic acid or acrylic acid can be polymerized while satisfying these requirements.
[0019]
Therefore, an object of the present invention is to provide an ester of a primary alcohol and a methacrylic acid or acrylic acid, which is generally easily deteriorated in polymerization performance as the methacrylic acid ester or acrylic acid ester in the anionic polymerization of methacrylic acid ester or acrylic acid ester. Use a polymerization initiator compound or its precursor compound that is relatively safe and easy to handle, use a hydrocarbon solvent that can be easily recovered and reused as a polymerization solvent, and compare the polymerization temperatures. Even when high temperature conditions (that is, relatively weak cooling conditions) are adopted, high initiation efficiency (block efficiency in the case of block copolymerization) and high living properties are achieved, so that a polymer with a narrow molecular weight distribution is achieved. In addition, block copolymer weight with less impurities such as homopolymers Producing body and is to provide a polymerization process capable. Another object of the present invention is to provide an industrially advantageous production method of a polymer using a polymerization method having such excellent advantages.
[0020]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventor performs anionic polymerization of methacrylic acid ester or acrylic acid ester in the presence of a specific organoaluminum compound using a specific polymerization initiator compound. Thus, the above-mentioned methacrylic acid ester or acrylic acid ester, the polymerization initiator compound (or its precursor compound) and the application scope of the polymerization solvent, the above-mentioned polymerization conditions (temperature conditions), and the above-mentioned polymerization results ( It was found that the starting efficiency and the living property are solved, and the present invention has been solved.
[0021]
That is, in the present invention, first, when anionic polymerization of a methacrylic acid ester or an acrylic acid ester using a polymerization initiator compound is carried out, 1,3-butadiene and isoprene With conjugated diene compounds Selected from polystyryllithium, poly-α-methylstyryllithium and butyllithium A tertiary compound using an addition reaction product with an organic alkali metal compound and containing in the polymerization system a chemical structure represented by the formula: Al-O-Ar (wherein Ar represents an aromatic ring) in the molecule. A polymerization method characterized by the presence of an organoaluminum compound.
[0022]
The second aspect of the present invention is a method for producing a polymer comprising polymerizing a methacrylic acid ester or an acrylic acid ester by the above polymerization method.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0024]
Methacrylic acid ester or acrylic acid ester (hereinafter, methacrylic acid ester and acrylic acid ester may be collectively referred to as “(meth) acrylic acid ester”) as a raw material in the polymerization method according to the present invention is not limited. Various types can be used. Specific examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, methacrylic acid. Esters of primary alcohol and methacrylic acid, such as methoxyethyl acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, trimethoxysilylpropyl methacrylate, trifluoromethyl methacrylate, trifluoroethyl methacrylate; Esters of secondary alcohols and methacrylic acid, such as isopropyl acid, cyclohexyl methacrylate, isobornyl methacrylate; tert-butyl methacrylate Such as Le, and esters of a tertiary alcohol and methacrylic acid. Specific examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and lauryl acrylate. , Esters of primary alcohols and acrylic acid, such as methoxyethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, glycidyl acrylate, trimethoxysilylpropyl acrylate, trifluoromethyl acrylate, trifluoroethyl acrylate, etc. Ester of secondary alcohol and acrylic acid such as isopropyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc .; tertiary alcohol such as tert-butyl acrylate and acrylic acid Ester and the like. Among the above (meth) acrylic acid esters, when an ester of a primary alcohol and methacrylic acid or acrylic acid is used, the effects of the present invention are particularly prominent.
[0025]
In the present invention, if necessary, other anionic polymerizable monomers can be used in addition to the (meth) acrylic acid ester as a raw material. Examples of the anionic polymerizable monomer that can be used optionally include trimethylsilyl methacrylate, N-isopropylmethacrylamide, N-tert-butylmethacrylamide, trimethylsilyl acrylate, N-isopropylacrylamide, N-tert-butylacrylamide, and the like. And methacrylic or acrylic monomers. In addition, a polyfunctional anionic polymerizable monomer (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate) containing two or more methacrylic or acrylic structures such as methacrylic acid ester structure and acrylic acid ester structure in the molecule. 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc.) Can also be used.
[0026]
In the polymerization method according to the present invention, monomers such as (meth) acrylic acid esters may be used alone or in combination of two or more. When two or more monomers are used in combination, the combination of the monomers, the addition timing of the monomers to the polymerization system (for example, two or more monomers are added at the same time, or at intervals) By selecting conditions such as whether to add them separately, it is possible to adopt an arbitrary copolymerization form such as random copolymerization, block copolymerization, and tapered block copolymerization. Since the polymerization method of the present invention is a polymerization method excellent in starting efficiency and living property, the effect is particularly remarkable in block copolymerization.
[0027]
In the polymerization method according to the present invention, polymerization of (meth) acrylic acid ester is performed.
[0028]
(A) In the presence of a tertiary organoaluminum compound containing in its molecule a chemical structure represented by the formula: Al-O-Ar (wherein Ar represents an aromatic ring)
[0029]
(B) using a polymerization initiator compound comprising an addition reaction product of a conjugated diene compound and an organic alkali metal compound,
[0030]
It is important to do. When both of the above conditions (A) and (B) are satisfied, the applicable range in (meth) acrylic acid ester, organic alkali metal compound and polymerization solvent is widened, and the cooling conditions during polymerization can be relaxed. Moreover, the polymerization results (starting efficiency and living property) can be improved.
[0031]
The polymerization initiator compound used in the present invention is a product obtained by addition reaction of a conjugated diene compound with an organic alkali metal compound.
[0032]
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, myrcene, 2-methyl-1,3-pentadiene, cyclohexadiene, and the like. Among these, in terms of excellent starting efficiency, 1,3-butadiene or isoprene is preferable, and 1,3-butadiene is particularly preferable.
[0033]
As the organic alkali metal compound, any alkali metal salt of an organic compound capable of nucleophilic addition to a conjugated diene compound can be used. As an alkali metal atom which an organic alkali metal compound has, lithium, potassium or sodium is preferable, and lithium is particularly preferable. In addition, the organic group corresponding to the portion obtained by removing one or more alkali metal atoms contained therein from the organic alkali metal compound is monovalent such as n-butyl, sec-butyl, tert-butyl, or the like. Divalent or higher saturated hydrocarbon group; monovalent or divalent or higher aromatic hydrocarbon group such as diphenylmethyl, 1,1-diphenyl-3-methylpentyl, 1,1-diphenylhexyl, triphenylmethyl, fluorenyl, etc. Is mentioned. The organic group may be a group in the form of a polymer (in the present specification, the term “polymer” includes the concept of “oligomer”), and thus its molecular weight is wide. Although not necessarily limited, it is generally in the range of 15 to 5,000,000.
Among organic alkali metal compounds, typical examples of monofunctional organic alkali metal compounds include low molecular weight organic monolithium compounds having a primary carbon atom as an anion center, such as n-butyllithium; sec-butyllithium, diphenylmethyllithium Low molecular weight organic monolithium compounds having a secondary carbon atom as an anion center, such as fluorenyl lithium; tert-butyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium, tri Low molecular weight organic monolithium compounds having a tertiary carbon atom as an anion center, such as phenylmethyllithium; chemistry in which a lithium atom is bonded to only one molecular chain terminal site, such as polystyryllithium and poly-α-methylstyryllithium List monolithium salts of polymers with a structure. Can. Among organic alkali metal compounds, typical examples of polyfunctional organic alkali metal compounds having two or more alkali metal atoms in the molecule include tetra-α-methylstyrenedilithium, 1,3-bis (1- Organic dilithium compounds such as lithio-1,3-dimethylpentyl) benzene and 1,3-bis (1-lithio-1-phenyl-3-methylpentyl) benzene; a low molecular weight organic monolithium compound reacted with divinylbenzene 2 or more such as an organic multi-lithium compound obtained (for example, a compound obtained by reacting sec-butyllithium as a low molecular weight organic monolithium compound and reacting with 0.5 or more moles of divinylbenzene) A lithium salt of a polymer having a chemical structure in which a lithium atom is bonded to the molecular chain terminal site; A polymer having a bond (for example, a conjugated diene polymer) is mixed with a low molecular weight organic monolithium compound (for example, sec-butyllithium) at a ratio of 2 moles or more to the Lewis base (for example, sec-butyllithium). N, N, N ′, N′-tetramethylethylenediamine, etc.) in the presence of N, N, N ′, N′-tetramethylethylenediamine, etc. Examples thereof include a multi-lithium salt of a polymer having a chemical structure in which lithium atoms are bonded in a pendant manner.
[0034]
Among the low molecular weight organic monolithium compounds mentioned above, low molecular weight organics having a secondary carbon atom or a primary carbon atom as an anion center in terms of high safety, good handleability, high starting efficiency, etc. Monolithium compounds are preferred, and sec-butyllithium and n-butyllithium are particularly preferred.
[0035]
As described above, a polymer lithium salt having a chemical structure in which a lithium atom is bonded only to one molecular chain terminal site, or a polymer lithium salt having a chemical structure in which a lithium atom is bonded to two or more molecular chain terminal sites Further, as a lithium salt of a polymer having a chemical structure in which a lithium atom is bonded to one or more molecular chain terminal sites, anionic polymerization of an anionic polymerizable monomer using a low molecular weight organic lithium compound as a polymerization initiator compound The so-called living polymer formed by the above can be used. When the organolithium compound used as the polymerization initiator compound is monofunctional, the formed living polymer is basically a monolithium salt of a linear polymer. Further, when the organolithium compound is bifunctional or more polyfunctional, the formed living polymer is basically a dilithium salt of a linear or star polymer or a multilithium salt higher than that. The anionic polymerizable monomer used to form such a living polymer is not necessarily limited, but aromatic such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, etc. Nonpolar or low polarity anionic polymerizable monomers such as vinyl compounds are preferred.
[0036]
As a precursor compound (organic alkali metal compound) for preparing a polymerization initiator compound for (meth) acrylate polymerization, a heavy compound having a chemical structure in which a lithium atom is bonded to one or more molecular chain terminal sites. When the lithium salt of the coalescence is used, the polymer obtained through the subsequent addition of the conjugated diene compound and the polymerization of the (meth) acrylic acid ester is a block copolymer. Further, when a polymer multi-lithium salt having a chemical structure in which one lithium atom is bonded to each of a plurality of sites in the polymer main chain in a pendant form is used as the precursor compound, a subsequent conjugated diene compound is used. The polymer obtained through the addition of and polymerization of (meth) acrylic acid ester is a graft copolymer.
[0037]
The polymerization initiator compound used in the polymerization of the (meth) acrylic acid ester according to the present invention is prepared by addition reaction of the conjugated diene compound with the organic alkali metal compound. The anion center in the product of such an addition reaction is a carbon atom derived from a conjugated diene compound. In the present invention, as the polymerization initiator compound for the polymerization of (meth) acrylic acid ester, the organic alkali metal compound is not used as it is, but converted into an addition reaction product with a conjugated diene compound. In combination with the presence of a tertiary organoaluminum compound having a chemical structure represented by the formula: Al-O-Ar (wherein Ar represents an aromatic ring) in the molecule in the polymerization system, (meth) It is possible to achieve the effects of the present invention such as expansion of application range in acrylic ester, organic alkali metal compound and polymerization solvent, relaxation of cooling conditions during polymerization, and improvement of polymerization results (starting efficiency and living property). Become.
[0038]
In the present invention, the reaction conditions for the addition reaction of the conjugated diene compound with the organic alkali metal compound are not necessarily limited, but the conjugated diene compound is usually an alkali metal atom (or an anion of the organic alkali metal compound). It is used at a ratio of equimolar or more to the ion center). For the purpose of more complete addition of the anion center of the organoalkali metal compound to the conjugated diene compound, the conjugated diene compound is twice the mole of the alkali metal atom (or anion center) of the organoalkali metal compound. It is preferable to use in the above ratio. The upper limit of the ratio of the conjugated diene compound to the organic alkali metal compound is not limited for the purpose of achieving the effects of the present invention. However, if the proportion of the conjugated diene compound used relative to the organoalkali metal compound increases, the polyconjugated diene compound chain becomes longer due to the anionic polymerization of the conjugated diene compound. Accordingly, it is preferable to appropriately set conditions. That is, when the purpose is to obtain a block copolymer or graft copolymer comprising a polymer fragment composed of a conjugated diene compound and a polymer fragment composed of a (meth) acrylic ester, the desired copolymer In consideration of the degree of polymerization of the conjugated diene compound in the coalescence, it is preferable to set the ratio of the conjugated diene compound to the organic alkali metal compound. In addition, if it is not desired to introduce a polymer fragment composed of a conjugated diene compound into the final target polymer, conditions that do not increase the use ratio of the conjugated diene compound relative to the organic alkali metal compound (for example, an organic alkali metal compound) It is preferable to employ a condition of a ratio of 50 times mol or less with respect to the alkali metal atom (or anion center).
[0039]
The reaction between the conjugated diene compound and the organic alkali metal compound is not necessarily limited, but is preferably performed in an organic solvent. As an organic solvent, although not necessarily limited, from the point of relatively high safety during chemical handling, the point that can also serve as an organic solvent in the polymerization of the next (meth) acrylic acid ester, etc., Aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene; saturated hydrocarbon solvents such as hexane, cyclohexane, and methylcyclohexane; halogenated hydrocarbon solvents such as chloroform, methylene chloride, and carbon tetrachloride; dimethyl phthalate Ester solvents such as are preferably used. These organic solvents may be used alone or in combination of two or more. When an organic solvent is used, the amount used can be appropriately adjusted according to the type of the organic alkali metal compound used, the molecular weight of the target polymerization initiator compound, the type of the organic solvent, etc., but the reaction proceeds smoothly. In general, it is preferable to use the organic solvent in a proportion within the range of 200 to 3000 parts by weight with respect to 100 parts by weight of the total amount of the organic alkali metal compound and the conjugated diene compound.
[0040]
In the reaction of the conjugated diene compound and the organic alkali metal compound according to the present invention, it is desirable to prevent water from being mixed into the reaction system as much as possible. Therefore, it is preferable to use chemical substances that do not contain water as much as possible, such as conjugated diene compounds and other arbitrary chemical substances (for example, organic solvents). In accordance with the above, deaeration and dehydration treatment can be performed in advance. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium.
[0041]
Furthermore, for example, it is preferable to perform the addition reaction under sufficient stirring conditions so that the reaction conditions in the reaction system become uniform.
[0042]
In the reaction between the organic alkali metal compound and the conjugated diene compound according to the present invention, the temperature of the reaction system is not particularly limited, and a suitable temperature condition is appropriately selected according to the type of the organic alkali metal compound, the type of the conjugated diene compound, and the like. It may be selected and adopted, but in many cases, it is preferable to employ a temperature within the range of −20 ° C. to 100 ° C. In addition, the reaction progresses based on a change in the color tone derived from the anion in the reaction system, or a quantitative analysis by an analytical means such as gas chromatography or nuclear magnetic resonance absorption spectrum (NMR) of a sample collected from the reaction system. While confirmation, it may be continued until the addition of the conjugated diene compound is completed, but the time required for the reaction is usually in the range of 1 minute to 24 hours.
[0043]
In the polymerization method according to the present invention, at least in the step of polymerizing the (meth) acrylic acid ester, a chemical structure represented by the formula: Al—O—Ar (wherein Ar represents an aromatic ring) is present in the molecule in the polymerization system. In the presence of a tertiary organoaluminum compound (hereinafter, the tertiary organoaluminum compound may be referred to as “organoaluminum compound (I)”). In the present invention, the organoaluminum compound (I) is selected and used as the organoaluminum compound present in the polymerization system of the (meth) acrylic acid ester, thereby adding the organoalkali metal compound and the conjugated diene compound. Combined with the use of a polymerization initiator compound consisting of the reaction product, expansion of the application range in (meth) acrylic acid ester, organic alkali metal compound and polymerization solvent, relaxation of cooling conditions during polymerization, and polymerization performance (starting efficiency and It is possible to achieve the effect of the present invention, that is, improvement in living property.
[0044]
The organoaluminum compound (I) is an organoaluminum compound having a chemical structure in which one of three bonds of an aluminum atom is bonded to an aromatic ring through an oxygen atom (hereinafter referred to as the organoaluminum compound). , An organic compound having a chemical structure in which two of the three bonds of an aluminum atom are bonded to an aromatic ring via an oxygen atom. An aluminum compound (hereinafter, the organoaluminum compound may be referred to as “organoaluminum compound (I-2)”), and three of the three bonds of the aluminum atom are aromatic rings via oxygen atoms. An organoaluminum compound having a chemical structure bonded to the organic aluminum compound (hereinafter referred to as “organoaluminum compound (I-3)”) It is roughly classified into three types is) referred.
[0045]
A typical chemical structure of the organoaluminum compound (I-2) or (I-3) has the general formula (A):
[0046]
[Chemical 1]
AlR ¹ R ² R ³ (A)
[0047]
(Wherein R ¹ Has a monovalent saturated hydrocarbon group that may have a substituent, a monovalent aromatic hydrocarbon group that may have a substituent, an alkoxy group that may have a substituent, and a substituent. An aryloxy group or an N, N-disubstituted amino group, which may be R ² And R ³ Each independently represents an aryloxy group which may have a substituent or R ² And R ³ Represents an aryleneoxy group which may be bonded to have a substituent. )
[0048]
It is represented by Moreover, the typical chemical structure of the organoaluminum compound (I-1) is represented by the general formula (B):
[0049]
[Chemical 2]
AlR ⁴ R ⁵ R ⁶ (B)
[0050]
(Wherein R ⁴ Represents an aryloxy group which may have a substituent, and R ⁵ And R ⁶ Are each independently a monovalent saturated hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent or N , N-disubstituted amino group. )
[0051]
It is represented by
[0052]
The organoaluminum compound (I) may be appropriately selected and used depending on the type of monomer such as (meth) acrylic acid ester to be used. The organoaluminum compound (I-2) or (I-3) is more preferable in terms of the height of the polymer, the living property at the time of polymerization, the relaxation of the cooling conditions at the time of polymerization, and the like.
[0053]
In the general formulas (A) and (B), R ¹ , R ² , R ³ And R ⁴ Examples of the aryloxy group which may have a substituent each of which may be represented by the formula: phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di-tert -Butylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butyl-4-ethylphenoxy group, 2 , 6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, aryloxy group having no substituent such as 1-pyrenyloxy group; and 7-methoxy-2-naphthoxy group, etc. And an aryloxy group having the following substituents. Among the aryloxy groups which may have a substituent, a substituted phenoxy group in which an alkyl group is bonded to each of the 2-position and the 6-position (for example, 2,6-dimethylphenoxy group, 2,6-di-tert- A butylphenoxy group, a 2,6-di-tert-butyl-4-methylphenoxy group, a 2,6-di-tert-butyl-4-ethylphenoxy group, etc.), and branched alkyl groups at the 2-position and 6-position, respectively. Are bonded to a phenoxy group (so-called hindered phenoxy group; for example, 2,6-di-tert-butylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 2,6-di- tert-butyl-4-ethylphenoxy group and the like are more preferable.
[0054]
In the general formula (A), R ² And R ³ Examples of the aryleneoxy group which may have a substituent which may be bonded to each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2′-methylenebis (4-methyl) -6-t-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2-naphthol and the like. The group of the form remove | excluding the hydrogen atom in a phenolic hydroxyl group can be mentioned.
[0055]
In addition, about the aryloxy group which may have said substituent, and the arylene oxy group which may have said substituent, when it has one or more substituents, as this substituent, methoxy group And alkoxy groups such as ethoxy group, isopropoxy group and tert-butoxy group; and halogen atoms such as chlorine and bromine.
[0056]
In the general formulas (A) and (B), R ¹ , R ⁵ And R ⁶ As monovalent saturated hydrocarbon groups that may each independently represent a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl Group, tert-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, alkyl group such as 2-ethylhexyl group; cycloalkyl group such as cyclohexyl group, etc. ¹ , R ⁵ And R ⁶ As the monovalent aromatic hydrocarbon group which may have a substituent which can be independently represented, an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; ¹ , R ⁵ And R ⁶ Examples of the alkoxy group that may have a substituent which can be independently represented include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, and the like. ¹ , R ⁵ And R ⁶ Examples of N, N-disubstituted amino groups that can be independently represented include dialkylamino groups such as dimethylamino group, diethylamino group and diisopropylamino group; bis (trimethylsilyl) amino group and the like. These monovalent saturated hydrocarbon groups, monovalent aromatic hydrocarbon groups, alkoxy groups and N, N-disubstituted amino groups each may have a methoxy group, an ethoxy group, an isopropoxy group. Groups, alkoxy groups such as tert-butoxy group, halogen atoms such as chlorine and bromine, and the like.
[0057]
R in the general formula (A) ¹ , R ² And R ³ As long as they are within the above definition, they may have the same chemical structure or different chemical structures. Similarly, R in the general formula (B) ⁵ And R ⁶ As long as they are within the above definition, they may have the same chemical structure or different chemical structures.
[0058]
Typical examples of the organoaluminum compound represented by the general formula (A) include ethylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-tert-butylphenoxy). ) Aluminum, ethyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2 , 6-Di-tert-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, n-octylbis (2,6-di-tert-butyl-4) -Methylphenoxy) aluminum, n-octylbis (2,6-di-t rt-butylphenoxy) aluminum, n-octyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, methoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum , Methoxybis (2,6-di-tert-butylphenoxy) aluminum, methoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, ethoxybis (2,6-di-tert-butyl) -4-methylphenoxy) aluminum, ethoxybis (2,6-di-tert-butylphenoxy) aluminum, ethoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, isopropoxybis ( 2,6-di-tert-butyl- 4-methylphenoxy) aluminum, isopropoxybis (2,6-di-tert-butylphenoxy) aluminum, isopropoxy [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, tert- Butoxybis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, tert-butoxybis (2,6-di-tert-butylphenoxy) aluminum, tert-butoxy [2,2′-methylenebis (4-methyl) -6-tert-butylphenoxy)] aluminum, tris (2,6-di-tert-butyl-4-methylphenoxy) aluminum, tris (2,6-diphenylphenoxy) aluminum and the like. Among these organoaluminum compounds represented by the general formula (A), isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-tert-butylphenoxy) Aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-tert-butylphenoxy)] aluminum, etc. are particularly preferable in terms of high starting efficiency, high living property, availability, ease of handling, etc. preferable.
[0059]
In addition, typical examples of the organoaluminum compound represented by the general formula (B) include diethyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum and diethyl (2,6-di-tert-butyl). Phenoxy) aluminum, diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-tert-butylphenoxy) aluminum, di-n-octyl (2,6-di-) tert-butyl-4-methylphenoxy) aluminum, di-n-octyl (2,6-di-tert-butylphenoxy) aluminum, and the like.
[0060]
The manufacturing method of the said organoaluminum compound (I) is not specifically limited, For example, it can manufacture according to a well-known method.
[0061]
In the present invention, only one type of organoaluminum compound (I) may be used, or two or more types may be used in combination.
[0062]
With respect to the amount of the organoaluminum compound (I) used in the present invention, a suitable amount is appropriately selected depending on the type of polymerization operation, the type of solvent constituting the polymerization system, and other various polymerization conditions when performing solution polymerization. In general, it is preferable to use the organoaluminum compound (I) in an equimolar ratio or more with respect to the alkali metal atom (or anion center) of the polymerization initiator compound to be used. It is more preferable to use at a molar ratio. In addition, after preparing a polymerization initiator compound using an organic alkali metal compound and a conjugated diene compound, when using substantially the entire amount of the polymerization initiator compound for polymerization of (meth) acrylic acid ester, use Since the number of moles of alkali metal atoms (or anion centers) in the prepared organic alkali metal compound and the number of moles of alkali metal atoms (or anion centers) in the prepared polymerization initiator compound are substantially the same, an organoaluminum compound ( I) is preferably used in a proportion of equimolar or more with respect to the alkali metal atom (or anion center) of the organic alkali metal compound used initially, and more preferably in a proportion of 2 to 100 times mol. .
[0063]
In the polymerization reaction according to the present invention, an ether compound; a tertiary polyamine compound; an inorganic salt such as lithium chloride; a metal alkoxide compound such as lithium methoxyethoxy ethoxide and potassium t-butoxide; Additives such as organic quaternary salts such as chloride and tetraethylphosphonium bromide may be present. In particular, when the ether compound or the tertiary polyamine compound is present, in the polymerization of the (meth) acrylic acid ester, the initiation efficiency (or block efficiency) and the polymerization rate can be further improved. It is preferable because the living property can be further improved by suppressing the activity.
[0064]
As long as the ether compound does not adversely affect the polymerization reaction, it should be used by appropriately selecting from compounds having an ether bond (—O—) in the molecule and not containing a metal component. However, in terms of high effects such as high starting efficiency and high living property during polymerization, a cyclic ether compound having two or more ether bonds in the molecule or one or more ether bonds in the molecule. A non-cyclic ether compound is preferable. Specific examples of the cyclic ether compound having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. Specific examples of the acyclic ether compound having one or more ether bonds in the molecule include acyclic monoether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1, 2-diisopropoxypropane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3 -Dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4 Acyclic diether compounds such as diethoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane; diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, diethylene glycol diethyl Acyclic triether compounds such as ether, dipropylene glycol diethyl ether, dibutylene glycol diethyl ether; triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, tribubutylene Glycol diethyl ether, tetraethylene glycol dimethyl Ether, tetrapropylene glycol dimethyl ether, tetrabutylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethyl ether, and dialkyl ethers of polyalkylene glycols such as tetraethylene butylene glycol diethyl ether. Among the specific examples of the above ether compounds, there is little adverse effect on the organoaluminum compound (I), and the effects of improving the polymerization rate, living property, starting efficiency (or block efficiency), etc. are particularly prominent and easy to obtain. In this respect, an acyclic ether compound is preferable, and diethyl ether or 1,2-dimethoxyethane is particularly preferable.
[0065]
When a cyclic ether compound having one ether bond in the molecule, such as an epoxy compound such as tetrahydrofuran or propylene oxide, is present in the polymerization system according to the present invention, it exhibits an excessively strong interaction with the organoaluminum compound (I). In some cases, it may directly react with the polymerization initiator compound or the living polymer during growth. In such a case, it is generally preferable to avoid the presence of the cyclic ether compound in the polymerization system at least in the polymerization step of the (meth) acrylic acid ester.
[0066]
As long as the above-mentioned tertiary polyamine compound does not adversely affect the polymerization reaction, it can be used by appropriately selecting from compounds having two or more tertiary amine structures in the molecule. In the present invention, the “tertiary amine structure” means a partial chemical structure in which three carbon atoms are bonded to one nitrogen atom, and the nitrogen atom is bonded to three carbon atoms. As long as it exists, it may constitute a part of the aromatic ring. Preferable specific examples of the tertiary polyamine compound include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ″, N ″. -Chain polyamine compounds such as pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexaamine Hydro-1,3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10 , 13,16-hexaazacyclooctadecane and other non-aromatic heterocyclic compounds; 2,2′-bipyridyl, 2,2 ′: 6 ′, 2 ″ -terpyridine and other aromatic heterocyclic compounds Goods and the like. In the case where the presence of a tertiary monoamine compound such as triethylamine into the polymerization system at least (meth) polymerization process of the acrylic acid ester, is less than or or effect effect is not substantially observed.
[0067]
A compound having one or more ether bonds and one tertiary amine structure in the molecule can be regarded as the above-mentioned ether compound, and one or more ether bonds and two or more three bonds in the molecule. The compound having a tertiary amine structure can be regarded as any one of the ether compound and the tertiary polyamine compound. Therefore, a compound having one or more ether bonds and one or more tertiary amine structures in the molecule can also be used as the ether compound or the tertiary polyamine compound.
[0068]
When the above ether compound or tertiary polyamine compound is used, the amount used is not necessarily limited. However, for the purpose of fully expressing the above effect based on addition, the ether compound and tertiary polyamine compound to be used are used. It is preferable that the total number of moles is a ratio that is at least 0.1 times the number of moles of the alkali metal atom or anion center of the polymerization initiator compound or precursor compound (eg, organic alkali metal compound) used. , More preferably 0.3 times or more, and even more preferably 0.5 times or more. The upper limit of the usage amount of the ether compound and tertiary polyamine compound is not necessarily limited, but if the usage amount is too large, the starting efficiency tends to decrease, so that the starting efficiency is not significantly reduced. In general, it is preferable to keep the total amount of the ether compound and the tertiary polyamine compound within a range of about 95% by weight or less based on the polymerization system.
[0069]
In the polymerization reaction according to the present invention, any polymerization form such as a solution polymerization method, a bulk polymerization method and a precipitation polymerization method can be adopted. However, it is possible to control the polymerization temperature, make the conditions in the polymerization system uniform, and the like. From the viewpoint of allowing the polymerization to proceed smoothly, it is preferable to employ a solution polymerization method in an organic solvent. The organic solvent is not necessarily limited, but it is generally high in safety when handling chemicals, hardly mixed into wastewater, and is easy to recover and purify the solvent. Aromatic hydrocarbon solvents such as toluene, ethylbenzene and xylene; saturated hydrocarbon solvents such as hexane, cyclohexane and methylcyclohexane; halogenated hydrocarbon solvents such as chloroform, methylene chloride and carbon tetrachloride; dimethyl phthalate, etc. An ester solvent or the like is preferably used. These organic solvents may be used alone or in combination of two or more.
[0070]
When an organic solvent is used, the amount used is the degree of polymerization of the target polymer, the type of monomer such as (meth) acrylic acid ester, the type of polymerization initiator compound, the type of organoaluminum compound (I) The organic solvent can be adjusted as appropriate depending on the type of the organic solvent, etc., but generally the organic solvent is used from the viewpoints of smooth progress of polymerization, ease of separation and acquisition of the produced polymer, reduction of waste liquid treatment burden, etc. The polymerization initiator compound and the monomer are preferably used in a proportion of 200 to 3000 parts by weight with respect to 100 parts by weight of the total amount of the monomers.
[0071]
In the polymerization reaction according to the present invention, it is desirable to prevent water from being mixed into the polymerization system as much as possible. Therefore, chemical substances supplied into the system such as monomer, organoaluminum compound (I), and any other chemical substances (for example, organic solvents, ether compounds, tertiary polyamine compounds, etc.) contain as much water as possible. It is preferable to use an untreated one, and for that purpose, it can be deaerated and dehydrated in advance if necessary. The polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, or helium.
[0072]
Furthermore, it is preferable to carry out the polymerization under sufficient stirring conditions, for example, so that the reaction conditions in the polymerization reaction system become uniform.
[0073]
The operation of the polymerization method of the present invention generally comprises a preparation operation of a polymerization initiator compound comprising addition reaction of a conjugated diene compound with an organic alkali metal compound, and (meth) acrylic acid using the polymerization initiator compound. It includes a polymerization operation of a (meth) acrylic acid ester comprising polymerizing an ester.
[0074]
The polymerization reaction according to the present invention is not necessarily limited, but a polymerization initiator compound is prepared by reacting a conjugated diene compound with an organic alkali metal compound, and then (meth) acrylic acid ester is added to the system. It is easy to do by doing. The addition time of the organoaluminum compound (I) at that time is not necessarily limited as long as the organoaluminum compound (I) can be present in the polymerization system of the (meth) acrylic acid ester. A method comprising adding the total amount of the organoaluminum compound (I) to the system containing the polymerization initiator compound at the stage before the addition of the ester, the total amount of the organoaluminum compound (I) being converted to (meth) acrylic acid ester A method comprising adding the organoaluminum compound (I) together with a (meth) acrylic acid ester to a system containing a polymerization initiator compound by mixing, a part of the organoaluminum compound (I) (meta ) Mixed with acrylic ester and the remainder of the organoaluminum compound (I) contains a polymerization initiator compound By adding a part of the organoaluminum compound (I) together with the (meth) acrylic acid ester into the system containing the polymerization initiator compound and the remainder of the organoaluminum compound (I). Various methods such as a method can be employed. Among the methods for adding the organoaluminum compound (I), a method comprising adding at least a part of the organoaluminum compound (I) to the (meth) acrylate and then adding it to the polymerization system is an organoaluminum. Suppression of side reaction by coordination of compound (I) to (meth) acrylic acid ester, suppression of deactivation of polymerization initiator compound by reaction with impurities in (meth) acrylic acid ester of organoaluminum compound (I), etc. It is preferable in that the effect is achieved.
[0075]
It should be noted that at the time when the organoaluminum compound (I) and the polymerization initiator compound are brought into contact with each other, it is preferable to control the temperature of the reaction system to 40 ° C. or less from the viewpoint of increasing the initiation efficiency of the polymerization initiator compound. More preferably, the temperature is controlled to be not higher than ° C.
[0076]
In addition, when the polymerization reaction of (meth) acrylic acid ester is performed in the presence of an ether compound or a tertiary polyamine compound, the addition time of the ether compound or tertiary polyamine compound is not necessarily limited, but the polymerization initiator compound and It is preferable to adopt a procedure that allows contact with the organoaluminum compound (I) prior to the contact.
[0077]
In the polymerization according to the present invention, the temperature of the reaction system is not particularly limited, and if a suitable temperature condition is appropriately selected according to the type of monomer to be polymerized, such as (meth) acrylic acid ester, and employed. In many cases, it is preferable to employ a temperature within the range of −60 ° C. to + 100 ° C., and it is more preferable to employ a temperature within the range of −50 ° C. to + 50 ° C. For example, when polymerizing a methacrylic acid ester, it is preferable to employ a temperature within a range of −40 ° C. to + 100 ° C., and more preferably a temperature within a range of −30 ° C. to + 50 ° C. Moreover, when polymerizing acrylic acid ester, it is preferable to employ | adopt the temperature within the range of -60 degreeC-+50 degreeC, and it is more preferable to employ | adopt the temperature within the range of -50 degreeC-+30 degreeC. In the polymerization method according to the present invention, the cooling conditions of the polymerization system can be relaxed as compared with the conventional anionic polymerization method, and high living property can be achieved even when polymerization is performed at a temperature closer to room temperature.
[0078]
In the (meth) acrylic acid ester polymerization reaction according to the present invention, a sample collected from the polymerization system is quantitatively analyzed by analysis means such as gas chromatography, gel permeation chromatography (GPC), nuclear magnetic resonance absorption spectrum (NMR) and the like. The reaction may be appropriately continued by confirming the progress of the polymerization, but the time required for the polymerization reaction is usually in the range of 1 minute to 24 hours.
[0079]
When the (meth) acrylic acid ester polymerization reaction according to the present invention is carried out in the presence of the ether compound or tertiary polyamine compound, the polymerization reaction rate can be further increased. That is, in the case of polymerization of methacrylic acid ester, the polymerization can be completed within several minutes, and in the case of polymerization of acrylic acid ester, the polymerization can be completed within tens of seconds. Therefore, when the polymerization reaction according to the present invention is performed in the presence of an ether compound or a tertiary polyamine compound, it is possible to adopt a “tubular continuous polymerization” method with high productivity and good cooling efficiency. is there.
[0080]
In the present invention, the polymerization reaction can be stopped by adding a polymerization terminator to the reaction mixture in accordance with a known anionic polymerization method at the stage where the target polymer chain is formed by the polymerization reaction. As the polymerization terminator, for example, a protic compound such as methanol, acetic acid, or a hydrochloric acid methanol solution can be used. Although the usage-amount of a polymerization terminator is not specifically limited, Generally, the ratio which becomes in the range of 1-100 times mole with respect to the alkali metal atom (or anion center) of a polymerization initiator compound is preferable.
[0081]
In the present invention, a terminal functional group-imparting agent (eg, aldehyde, lactone, carbon dioxide, etc.) is added to the reaction system after the completion of all the predetermined polymerizations and before the addition of the polymerization terminator. In this case, a polymer having a functional group such as a hydroxyl group or a carboxyl group at the end of the molecular chain can be obtained. In addition, two or more functional groups such as formyl group, keto group, chlorocarbonyl group, and silyl halide group are present in the molecule after the completion of the predetermined polymerization and before the addition of the polymerization terminator. A polyfunctional compound may be added to the reaction system, and in that case, two or more polymers are formed by coupling (coupling) around the residue derived from the polyfunctional compound. A linear or star polymer can also be obtained.
[0082]
If the metal component derived from the used polymerization initiator compound or organoaluminum compound (I) remains in the polymer obtained by separation from the reaction mixture after termination of the polymerization, the physical properties of the polymer and the material using it Therefore, depending on the intended use of the polymer, it is preferable to remove the polymerization initiator compound and the metal compound derived from the organoaluminum compound (I) after completion of the polymerization. As a method for removing the metal compound, it is effective to subject the polymer to a cleaning treatment such as a washing treatment using an acidic aqueous solution or an adsorption treatment using an adsorbent such as an ion exchange resin. Here, as acidic aqueous solution, hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution etc. can be used, for example.
[0083]
The method for separating and obtaining the polymer from the reaction mixture after stopping the polymerization is not particularly limited, and any method according to a known method can be adopted. For example, a method of pouring the reaction mixture into a poor solvent of the polymer to precipitate the polymer, a method of distilling off the solvent from the reaction mixture and obtaining a polymer can be employed.
[0084]
Moreover, according to the present invention, a polymer having an arbitrary molecular weight can be produced. Although the molecular weight of the polymer that can be produced is in a wide range, in general, the number average molecular weight is preferably in the range of 1,000 to 1,000,000 from the viewpoint of the handleability, fluidity, mechanical properties and the like of the resulting polymer. In addition, according to the present invention, a polymer having high molecular weight uniformity (that is, a narrow molecular weight distribution) is usually obtained, and a polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less is produced. It is possible. However, a polymer having a wide molecular weight distribution can be intentionally obtained by controlling the rate of addition of the monomer to the polymerization system, the diffusion rate of the monomer in the polymerization system, and the like.
[0085]
【Example】
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.
[0086]
In the following examples and the like, chemical substances that were dried and purified by a conventional method and deaerated with nitrogen were used. The chemical substances were transferred and supplied in a nitrogen atmosphere.
[0087]
Example 1 (Synthesis example of styrene-tert-butyl methacrylate block copolymer)
In this example, a process for preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene, a process for preparing a polymerization initiator compound by addition reaction of butadiene, and diisobutyl (2,6-di-tert-butyl-4) -Methylphenoxy) This is a production example of a styrene-tert-butyl methacrylate block copolymer comprising a polymerization step of tert-butyl methacrylate in the presence of aluminum (organoaluminum compound). In addition, the block efficiency (starting efficiency in the polymerization of tert-butyl methacrylate) is determined by utilizing the fact that the styrene polymer has UV absorption but the tert-butyl methacrylate polymer does not have UV absorption. It was.
[0088]
(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this was added 25 ml cyclohexane and 1.0 ml cyclohexane solution containing 0.13 mmol sec-butyllithium. To this solution, 2.0 g of styrene was added and stirred at 40 ° C. for 3 hours to prepare a polystyryllithium-containing solution.
[0089]
(2) When 0.20 ml of a cyclohexane solution containing 0.30 mmol of butadiene was added at 40 ° C. to the solution in the Schlenk tube obtained in (1) above, the color immediately faded from orange to colorless. Stirring was continued for 10 minutes at the same temperature.
About 0.5 ml of the obtained reaction mixture was sampled and analyzed by gas chromatography (hereinafter referred to as “GC”), and it was found that the reaction rate of butadiene and styrene was 99% or more. Moreover, as a result of analysis by GPC (polystyrene conversion), the peak top molecular weight (Mt) of the resulting addition reaction product of polystyryllithium and butadiene is 17100, and the number average molecular weight (Mn) is 16400. The weight average molecular weight / number average molecular weight ratio (Mw / Mn) was found to be 1.03.
[0090]
(3) The solution in the Schlenk tube obtained in (2) above is cooled to 15 ° C., and a toluene solution containing 0.65 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum 0.81 ml was added and stirred for 10 minutes.
Next, 1.0 g of tert-butyl methacrylate was added to the resulting solution while stirring vigorously. Polymerization was carried out with stirring at 15 ° C. for 5 hours, and then about 0.05 ml of methanol was added to terminate the polymerization.
As a result of sampling and GC analysis of a part of the obtained reaction mixture, it was found that the polymerization rate of tert-butyl methacrylate was 100%.
The polymer was acquired by removing the solvent in the obtained reaction liquid mixture by a vacuum drying method. As a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer is a block copolymer of Mt = 29100 and a polymer derived from a polymerization initiator compound of Mt = 18000 (polystyrene having a butadiene fragment at the terminal). The former: latter weight ratio was found to be 73:27. From this, it was found that the block efficiency in block copolymerization was 73%.
[0091]
Comparative Example 1
Anionic polymerization of styrene in the same manner as in Example 1 except that diethylbutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was used as the organoaluminum compound instead of triethylaluminum in the same mole number. Preparation of polystyryllithium by cis, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of tert-butyl methacrylate in the presence of an organoaluminum compound were sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mt was 16,900, Mn was 16,200, and Mw / Mn was 1.03.
After the polymerization step of tert-butyl methacrylate, the obtained reaction mixture was analyzed by GC. As a result, it was found that the polymerization rate of tert-butyl methacrylate was almost 100%.
The polymer obtained after removal of the solvent is derived from GPC-UV (254 nm) measurement (polystyrene conversion), high molecular weight components of Mt = 34100 and Mn = 35700, and polymerization initiator compound of Mt = 17400, Mn = 16600. It was found that the weight ratio of the former: the latter was 63:37 (polystyrene having a butadiene fragment at the end). The peak area ratio of the high molecular weight component is almost the same between the measurement result with the GPC-UV detector and the measurement result with the GPC-RI detector, and Mt of the high molecular weight component is derived from the polymerization initiator compound. Therefore, the main component of the high molecular weight component is a dimer of the polymerization initiator compound (the two polymerization initiator compound anions are found on the carbonyl group of one tert-butyl methacrylate). It is presumed that it is a coupling body obtained by nuclear addition. From this, it was found that the main component of the obtained polymer was polystyrene containing a butadiene fragment.
[0092]
Comparative Example 2
The anion of styrene was the same as in Example 1 except that diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was used as the organoaluminum compound in place of the same number of moles of triisobutylaluminum. Preparation of polystyryl lithium by polymerization, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of tert-butyl methacrylate in the presence of an organoaluminum compound were sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mt was 17400, Mn was 16800, and Mw / Mn was 1.03.
After the polymerization step of tert-butyl methacrylate, the obtained reaction mixture was analyzed by GC. As a result, it was found that the polymerization rate of tert-butyl methacrylate was almost 100%.
The polymer obtained after removal of the solvent is derived from GPC-UV (254 nm) measurement (polystyrene conversion), a high molecular weight component of Mt = 34800 and Mn = 37300, and a polymerization initiator compound of Mt = 18200 and Mn = 17500. It was found that the weight ratio of the former: the latter was 51:49 (polystyrene having a butadiene fragment at the end). The peak area ratio of the high molecular weight component is almost the same between the measurement result with the GPC-UV detector and the measurement result with the GPC-RI detector, and Mt of the high molecular weight component is derived from the polymerization initiator compound. Therefore, the main component of the high molecular weight component is a dimer of the polymerization initiator compound (the two polymerization initiator compound anions are found on the carbonyl group of one tert-butyl methacrylate). It is presumed that it is a coupling body obtained by nuclear addition). From this, it was found that the main component of the obtained polymer was polystyrene containing a butadiene fragment.
From the results of Example 1 and Comparative Examples 1 and 2, methacrylic acid in the presence of an organoaluminum compound using a polymerization initiator compound consisting of an addition reaction product of an organic alkali metal compound and a conjugated diene compound was used. In the polymerization of the ester, when a trialkylaluminum, which is a common organoaluminum compound, is used (Comparative Examples 1 and 2), the organoaluminum compound is used even under polymerization conditions such that the polymerization does not proceed. When the above-mentioned specific organoaluminum compound (I) is used (Example 1), it can be seen that the polymerization can be carried out with high initiation efficiency (block efficiency).
[0093]
Example 2 (Synthesis example of styrene-methyl methacrylate block copolymer)
In this example, a process for preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene, a process for preparing a polymerization initiator compound by addition reaction of butadiene, and diisobutyl (2,6-di-tert-butyl-4) -Methylphenoxy) Production example of a styrene-methyl methacrylate block copolymer comprising a polymerization step of methyl methacrylate in the presence of aluminum (organoaluminum compound).
[0094]
(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this was added 25 ml of toluene and 0.12 ml of a cyclohexane solution containing 0.15 mmol of sec-butyllithium. To this solution, 0.75 g of styrene was added and stirred at 23 ° C. for 1.5 hours to prepare a polystyryllithium-containing solution.
[0095]
(2) When 0.40 ml of a cyclohexane solution containing 0.60 mmol of butadiene was added at 23 ° C. to the solution in the Schlenk tube obtained in (1) above, the color immediately faded from orange to colorless. Stirring was continued for 10 minutes at the same temperature.
As a result of sampling and GC analysis of a part of the obtained reaction mixture, it was found that the reaction rate of butadiene and styrene was 99% or more. Further, as a result of analysis by GPC (polystyrene conversion), it was found that Mn of the obtained addition reaction product of polystyryllithium and butadiene was 5700 and Mw / Mn was 1.03.
[0096]
(3) The solution in the Schlenk tube obtained in (2) above is cooled to −30 ° C., and toluene containing 0.80 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum 1.0 ml of solution was added and stirred for 10 minutes.
Next, 2.25 g of methyl methacrylate was added to the resulting solution with vigorous stirring. Polymerization was carried out at −30 ° C. for 2 hours with stirring, and then the polymerization was stopped by adding about 0.05 ml of methanol.
The obtained reaction mixture was reprecipitated in 300 ml of methanol to obtain a polymer. The yield of the obtained polymer was almost 100%. As a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 23300, Mw / Mn = 1.05, and a polymer derived from a polymerization initiator compound (terminal butadiene fragment) The weight ratio of the former: the latter was found to be 96: 4. From this, it was found that the block efficiency in block copolymerization was 96%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0097]
Example 3 (Synthesis example of styrene-methyl methacrylate block copolymer)
The addition temperature of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, the addition temperature of methyl methacrylate and the polymerization temperature were changed from -30 ° C to 0 ° C, and the polymerization time of methyl methacrylate was changed. Except for changing from 2 hours to 1 hour, in the same manner as in Example 2, preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of butadiene, and methacrylic acid in the presence of an organoaluminum compound Polymerization of methyl acid was sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5200 and Mw / Mn was 1.03.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 23600 and Mw / Mn = 1.06, and a dimer of the polymerization initiator compound (two A compound obtained by nucleophilic addition of a polymerization initiator compound anion to one carbonyl group of methyl methacrylate) and a polymer derived from the polymerization initiator compound (polystyrene having a butadiene fragment at the terminal). And their weight ratio was found to be 85: 6: 9. From this, it was found that the block efficiency in block copolymerization was 85%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0098]
Example 4 (Synthesis example of styrene-methyl methacrylate block copolymer)
Preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of isoprene, except that butadiene was used as the conjugated diene compound instead of butadiene, in the same manner as in Example 2. And polymerization of methyl methacrylate in the presence of an organoaluminum compound was sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5300 and Mw / Mn was 1.04.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 24500 and Mw / Mn = 1.07, and a dimer of the polymerization initiator compound (two A compound obtained by nucleophilic addition of a polymerization initiator compound anion to one methyl methacrylate carbonyl group) and a polymer derived from the polymerization initiator compound (polystyrene having an isoprene fragment at the end). And their weight ratio was found to be 80: 8: 12. From this, it was found that the block efficiency in block copolymerization was 80%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0099]
Example 5 (Synthesis example of styrene-methyl methacrylate block copolymer)
Instead of 1.0 ml of toluene solution containing 0.80 mmol diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum, 0.80 mmol isobutyl bis (2,6-di-tert-butyl) -4-methylphenoxy) By anionic polymerization of styrene in the same manner as in Example 3 except that a solution prepared by mixing 1.0 ml of a toluene solution containing aluminum and 0.22 g of 1,2-dimethoxyethane was used. Preparation of polystyryl lithium, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5500 and Mw / Mn was 1.03.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to have a block copolymer of Mn = 23800, Mw / Mn = 1.06, and a polymer derived from a polymerization initiator compound (at the end). It was found that the weight ratio of the former: the latter was 93: 7. From this, it was found that the block efficiency in block copolymerization was 93%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0100]
Comparative Example 3
Instead of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum as the organoaluminum compound, the same mole number of triethylaluminum was used, and the polymerization time of methyl methacrylate was changed from 2 to 24 hours. In the same manner as in Example 2, except for extending to styrene, the preparation of polystyryllithium by anionic polymerization of styrene, the preparation of a polymerization initiator compound by addition reaction of butadiene, and the polymerization of methyl methacrylate in the presence of an organoaluminum compound. We went sequentially.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5600 and Mw / Mn was 1.03.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 49800, Mw / Mn = 1.14, and a dimer of the polymerization initiator compound (two A compound obtained by nucleophilic addition of a polymerization initiator compound anion to one carbonyl group of methyl methacrylate) and a polymer derived from the polymerization initiator compound (polystyrene having a butadiene fragment at the terminal). And their weight ratio was found to be 37:42:21. From this, it was found that the block efficiency in block copolymerization was 37%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0101]
Comparative Example 4
Preparation of polystyryllithium by anionic polymerization of styrene, polymerization initiator by addition reaction of butadiene, in the same manner as in Comparative Example 3, except that triisobutylaluminum in the same mole number was used instead of triethylaluminum as the organoaluminum compound Preparation of the compound and polymerization of methyl methacrylate in the presence of the organoaluminum compound were sequentially performed.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5100 and Mw / Mn was 1.04.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 41900 and Mw / Mn = 1.12. A compound obtained by nucleophilic addition of a polymerization initiator compound anion to one carbonyl group of methyl methacrylate) and a polymer derived from the polymerization initiator compound (polystyrene having a butadiene fragment at the terminal). And their weight ratio was found to be 41:35:24. From this, it was found that the block efficiency in block copolymerization was 41%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0102]
Comparative Example 5
Example 2 except that polystyryllithium was used as a polymerization initiator compound for methyl methacrylate without subjecting it to an addition reaction using butadiene, and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours. In the same manner as above, the preparation of polystyryllithium by anionic polymerization of styrene and the polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. When diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added to a polystyryllithium-containing solution prepared by anionic polymerization of styrene, the color of the solution was the growth terminal of polystyrene. The orange color derived from the anion disappeared and became colorless. This change in color suggests that the added organoaluminum compound formed an art complex with the polystyrene growth terminal anion.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound (polystyryllithium), it was found that Mn was 5100 and Mw / Mn was 1.04.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. ¹ As a result of 1 H-NMR analysis, it was found that the polymerization rate of methyl methacrylate was about 6% and almost no polymerization was performed. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), it was found that the polymer was a polymer derived from a polymerization initiator compound (polystyrene).
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0103]
Comparative Example 6
In the step of preparing a polymerization initiator compound by addition reaction of butadiene, 0.60 ml of a cyclohexane solution containing 0.60 mmol of 1,1-diphenylethylene was added to a polystyryllithium-containing solution prepared by anionic polymerization of styrene. Anionic polymerization of styrene in the same manner as in Example 2 except that the process was changed to a process for preparing a polymerization initiator compound comprising reacting at 6 ° C. for 6 hours and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours. Preparation of polystyryllithium by the above, preparation of a polymerization initiator compound by addition reaction of 1,1-diphenylethylene, and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. The color of the polystyryllithium-containing solution changed from orange to deep red after the addition of 1,1-diphenylethylene. This phenomenon suggests that 1,1-diphenylethylene was capped at the end of polystyrene and the terminal anion was changed to 1,1-diphenylmethylene anion. In addition, the color of the polymerization initiator compound-containing solution is changed from orange to dark red derived from 1,1-diphenylmethylene anion after addition of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum. changed. This phenomenon suggests that the added organoaluminum compound formed an art complex with the 1,1-diphenylmethylene anion.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5600 and Mw / Mn was 1.03.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 38800, Mw / Mn = 1.07, and a dimer of two polymerization initiator compounds (two A compound that is estimated to be a coupling product obtained by nucleophilic addition of a polymerization initiator compound anion to one carbonyl group of methyl methacrylate, and a polymer derived from the polymerization initiator compound (terminal 1,1-diphenylethylene) It was found that their weight ratio was 54: 9: 33. From this, it was found that the block efficiency in block copolymerization was 54%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0104]
Comparative Example 7
Preparation of polymerization initiator compound by addition reaction of butadiene, polymerization start consisting of adding 1.8 mmol of α-methylstyrene to a polystyryllithium-containing solution prepared by anionic polymerization of styrene and reacting at 50 ° C. for 3 hours Preparation of polystyryllithium by anionic polymerization of styrene, α-methylstyrene, in the same manner as in Example 2, except that the preparation process of the agent compound was changed and the polymerization time of methyl methacrylate was extended from 2 hours to 3 hours Preparation of a polymerization initiator compound by addition reaction of methyl methacrylate and polymerization of methyl methacrylate in the presence of an organoaluminum compound were sequentially performed. The color of the polystyryllithium-containing solution changed from orange to dark red after the addition of α-methylstyrene. This phenomenon suggests that α-methylstyrene was capped at the end of polystyrene and the terminal anion was changed to α-methylstyryl anion. The color of the polymerization initiator compound-containing solution changed from dark red derived from α-methylstyryl anion to orange after addition of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum. . This phenomenon suggests that the added organoaluminum compound formed an art complex with the α-methylstyryl anion.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 6100 and Mw / Mn was 1.04.
After the polymerization step of methyl methacrylate, a polymer was obtained by reprecipitation. ¹ As a result of 1 H-NMR analysis, it was found that the polymerization rate of methyl methacrylate was about 3% and almost no polymerization was performed. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), it was found that the polymer was a polymer derived from a polymerization initiator compound (polystyrene).
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 1 below.
[0105]
[Table 1]

[0106]
In Table 1 above, the symbols in the columns of “organoaluminum compound” and “additive” mean the following compounds.
[0107]
iB ₂ Al (BHT): Diisobutyl (2,6-di-t-butyl-4-methylphenoxy) aluminum
iBAl (BHT) ₂ : Isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum
Et ₃ Al: Triethylaluminum
iB ₃ Al: Triisobutylaluminum
DME: 1,2-dimethoxyethane
[0108]
From the results of Examples 2 to 5 shown in Table 1 above, when polymerizing a methacrylic acid ester in the presence of an organoaluminum compound using an anionic polymerization initiator compound, polystyryllithium was used as the anionic polymerization initiator compound. When an addition reaction product of an organoalkali metal compound and a conjugated diene compound is used, and the specific organoaluminum compound (I) is used as the organoaluminum compound, a high starting efficiency (block efficiency) ) Can be achieved. On the other hand, from the results of Comparative Examples 3 to 7 described in Table 1, when trialkylaluminum, which is a general organoaluminum compound, is used as the organoaluminum compound (Comparative Examples 3 and 4), the starting efficiency (Block efficiency) is low, and an organic alkali metal compound such as polystyryl lithium as an anionic polymerization initiator compound is used as it is or in the form of an addition reaction product with an unsaturated compound other than a conjugated diene compound. In the case (Comparative Examples 5 to 7), it can be seen that the polymerization rate is extremely low or the starting efficiency (block efficiency) is low.
[0109]
Example 6 (Synthesis example of styrene-n-butyl acrylate block copolymer)
In this example, a process for preparing polystyryllithium (organic alkali metal compound) by anionic polymerization of styrene, a process for preparing a polymerization initiator compound by addition reaction of butadiene, and isobutylbis (2,6-di-tert-butyl- This is a production example of a styrene-n-butyl acrylate block copolymer comprising a polymerization step of n-butyl acrylate in the presence of 4-methylphenoxy) aluminum (organoaluminum compound). The block efficiency in block copolymerization (starting efficiency in polymerization of n-butyl acrylate) is calculated based on the polystyrene-equivalent number average molecular weight obtained by GPC measurement of the block copolymer, the amount used, and the yield. It was determined from the ratio to the molecular weight of the block copolymer.
[0110]
The addition temperature of a solution prepared by mixing a toluene solution containing isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum and 1,2-dimethoxyethane was changed from 0 ° C to -30 ° C. And instead of adding 2.25 g of methyl methacrylate at 0 ° C. and polymerizing at 0 ° C. for 1 hour, 2.25 g of n-butyl acrylate was added at −30 ° C. and polymerized at −30 ° C. for 5 minutes. In the same manner as in Example 5, except that the preparation of polystyryllithium by anionic polymerization of styrene, the preparation of a polymerization initiator compound by addition reaction of butadiene, and the polymerization of n-butyl acrylate in the presence of an organoaluminum compound were sequentially performed. went.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5000 and Mw / Mn was 1.04.
After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. In addition, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 21500, Mw / Mn = 1.09, and a polymer derived from a polymerization initiator compound (at the end). It was found that the weight ratio of the former: the latter was 96: 4.
Based on the molecular weight of the polymerization initiator polymer, the molecular weight of the block copolymer and the yield, the block efficiency was estimated to be 91%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 2 below.
[0111]
Example 7 (Synthesis example of styrene-n-butyl acrylate block copolymer)
Add a solution prepared by mixing 1.0 ml of toluene solution containing 0.80 mmol of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum and 0.22 g of 1,2-dimethoxyethane Instead of adding only 0.50 ml of a toluene solution containing 0.40 mmol of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum and adding n-butyl acrylate alone A solution prepared by mixing n-butyl acrylate of the same weight with 0.50 ml of a toluene solution containing 0.40 mmol of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum And the polymerization time of n-butyl acrylate was changed from 5 minutes to 30 minutes. In the same manner as in Example 6, preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of n-butyl acrylate in the presence of an organoaluminum compound were sequentially performed. It was.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5100 and Mw / Mn was 1.02.
After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. The yield of the obtained polymer was almost 100%. Further, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), the polymer was found to be a block copolymer of Mn = 24000 and Mw / Mn = 1.12 and a polymer derived from a polymerization initiator compound (at the end). It was found that the weight ratio of the former: the latter was 93: 7.
Based on the molecular weight of the polymerization initiator polymer, the molecular weight of the block copolymer and the yield, the block efficiency was estimated to be 81%.
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 2 below.
[0112]
Comparative Example 8
Instead of isobutylbis (2,6-di-tert-butyl-4-methylphenoxy) aluminum, the same number of moles of triisobutylaluminum was used, and the polymerization time of n-butyl acrylate was changed from 5 minutes to 6 hours. In the same manner as in Example 6 except for the change, preparation of polystyryllithium by anionic polymerization of styrene, preparation of a polymerization initiator compound by addition reaction of butadiene, and polymerization of n-butyl acrylate in the presence of an organoaluminum compound Were performed sequentially.
As a result of GPC (polystyrene conversion) analysis on the obtained polymerization initiator compound, it was found that Mn was 5800 and Mw / Mn was 1.04.
After the polymerization step of n-butyl acrylate, a polymer was obtained by reprecipitation. About the resulting polymer ¹ As a result of 1 H-NMR analysis, it was found that n-butyl acrylate was not polymerized at all. Moreover, as a result of GPC-UV (254 nm) measurement (polystyrene conversion), it was found that the polymer was a polymer derived from a polymerization initiator compound (polystyrene having a butadiene fragment at the terminal).
The chemical substances used, the polymerization conditions employed and the results obtained are shown in Table 2 below.
[0113]
[Table 2]

[0114]
In Table 2 above, the symbols in the columns of “organoaluminum compound” and “additive” have the following meanings.
iBAl (BHT) ₂ : Isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum
iB ₃ Al: Triisobutylaluminum
DME: 1,2-dimethoxyethane
a): added in the form of a mixture with n-butyl acrylate
[0115]
From the results shown in Table 2 above, when the acrylic acid ester is polymerized in the presence of an organoaluminum compound using a polymerization initiator compound consisting of an addition reaction product of an organic alkali metal compound and a conjugated diene compound, When the above-mentioned specific organoaluminum compound (I) is used as the organoaluminum compound (Examples 6 and 7), high starting efficiency (block efficiency) can be achieved, but trialkyl which is a general organoaluminum compound It can be seen that the polymerization reaction does not proceed when aluminum is used (Comparative Example 8).
[0116]
Example 8 (Synthesis example of methyl methacrylate polymer)
In this example, oligobutadienyl lithium (polymerization initiator compound) was prepared by addition reaction of a small proportion of butadiene to sec-butyllithium (organic alkali metal compound), and diisobutyl (2,6-di-tert- It is a manufacture example of the methyl methacrylate polymer which consists of a polymerization process of methyl methacrylate in presence of butyl-4-methylphenoxy) aluminum (organoaluminum compound). In addition, the starting efficiency in the polymer of methyl methacrylate is the molecular weight of the methyl methacrylate polymer calculated based on the polystyrene-equivalent number average molecular weight obtained by GPC measurement of the methyl methacrylate polymer, the amount used, and the yield. It was calculated from the ratio.
[0117]
(1) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this was added 18.5 ml of a cyclohexane solution containing 1.2 g of butadiene and cooled to 0 ° C. To this solution, 1.6 ml of a cyclohexane solution of sec-butyllithium having a concentration of 1.3 M was added, and the reaction was performed with stirring at 0 ° C. for 24 hours.
As a result of GPC measurement on the obtained reaction mixture, oligobutadienyl lithium having a polystyrene-equivalent number average molecular weight (Mn) of 1200 and a molecular weight distribution (Mw / Mn) of 1.18 is generated. I understood.
[0118]
(2) A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this, 15 ml of toluene and 1.5 ml of a cyclohexane solution of oligobutadienyllithium having a concentration of 0.1 M prepared in (1) above were added. The solution was cooled to −30 ° C., 1.0 ml of a toluene solution containing 0.80 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added, and the mixture was stirred for 10 minutes.
Next, 1.50 g of methyl methacrylate was added to the resulting solution while stirring vigorously. Polymerization was carried out at −30 ° C. for 2 hours with stirring, and then the polymerization was stopped by adding about 0.05 ml of methanol.
The obtained reaction mixture was reprecipitated in 300 ml of methanol to obtain a polymer. The yield of the obtained polymer was almost 100%. As a result of GPC measurement (polystyrene conversion), it was found that the polymer had Mn = 11900 and Mw / Mn = 1.07.
From these, it was found that the initiation efficiency in the polymerization of methyl methacrylate was 93%.
Table 3 below shows the chemical substances used, the polymerization conditions employed, and the results obtained.
[0119]
Comparative Example 9
A magnetic stirrer chip was placed in a 50 ml Schlenk tube with a three-way cock, and the inside of the container was purged with nitrogen. To this was added 15 ml of toluene, and after cooling to -30 ° C, 0.95 ml of a cyclohexane solution of tert-butyllithium having a concentration of 1.6 M was added. This solution was kept at −30 ° C., and 1.0 ml of a toluene solution containing 0.80 mmol of diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum was added and stirred for 10 minutes.
Next, 1.50 g of methyl methacrylate was added to the resulting solution while stirring vigorously. Polymerization was carried out at −30 ° C. for 2 hours with stirring, and then the polymerization was stopped by adding about 0.05 ml of methanol.
The obtained reaction mixture was reprecipitated in 300 ml of methanol to obtain a polymer. The yield of the obtained polymer was almost 100%. As a result of GPC measurement (polystyrene conversion), it was found that the polymer had Mn = 13000 and Mw / Mn = 1.11.
From these, it was found that the initiation efficiency in the polymerization of methyl methacrylate was 77%.
Table 3 below shows the chemical substances used, the polymerization conditions employed, and the results obtained.
[0120]
Comparative Example 10
Instead of 0.95 ml of 1.6M tert-butyllithium cyclohexane solution, 1.15 ml of 1.3M sec-butyllithium cyclohexane solution was used, and the polymerization time of methyl methacrylate was 2 to 6 hours. The polymerization of methyl methacrylate in the presence of an organoaluminum compound was tried in the same manner as in Comparative Example 9 except that the polymerization was continued.
However, it was found that methyl methacrylate was not polymerized.
Table 3 below shows the chemical substances used, the polymerization conditions employed, and the results obtained.
[0121]
Comparative Example 11
Instead of 0.95 ml of 1.6M tert-butyllithium in cyclohexane, 1.0 ml of 1.5M n-butyllithium in cyclohexane was used, and the polymerization time of methyl methacrylate was 2 to 6 hours. The polymerization of methyl methacrylate in the presence of an organoaluminum compound was tried in the same manner as in Comparative Example 9 except that the polymerization was continued.
However, it was found that methyl methacrylate was not polymerized.
Table 3 below shows the chemical substances used, the polymerization conditions employed, and the results obtained.
[0122]
[Table 3]

[0123]
In Table 3 above, the symbols in the column of “organoaluminum compound” mean the following compounds.
[0124]
iB ₂ Al (BHT): Diisobutyl (2,6-di-t-butyl-4-methylphenoxy) aluminum
[0125]
From the results of Example 8 shown in Table 3 above, using an anionic polymerization initiator compound as the methacrylic acid ester, one of the three bonds of the aluminum atom is an aromatic ring via an oxygen atom. When the polymerization is carried out in the presence of an organoaluminum compound having a chemical structure bonded to an anionic polymerization initiator compound, an addition reaction product of an organic alkali metal compound such as a low molecular weight alkyl lithium and a conjugated diene compound is used. It can be seen that a high starting efficiency can be achieved when used. On the other hand, from the results of Comparative Examples 9 to 11 described in Table 3, when a general polymerization initiator compound such as a low molecular weight alkyl lithium was used as it was as the anionic polymerization initiator compound, the polymerization rate was Is very low or the starting efficiency is low.
[0126]
Example 9 (Synthesis example of butadiene-methyl methacrylate diblock copolymer)
In this example, a process for preparing a living anion (polybutadienyl lithium; polymerization initiator compound) of polybutadiene by addition reaction (polymerization) of a large amount of butadiene to sec-butyllithium (organic alkali metal compound), and isobutylbis This is a production example of a butadiene-methyl methacrylate diblock copolymer comprising a polymerization step of methyl methacrylate in the presence of (2,6-di-t-butyl-4-methylphenoxy) aluminum (organoaluminum compound).
(1) The inside of a 1 liter autoclave was purged with nitrogen, and 520 g of toluene and 2.5 ml of a cyclohexane solution of sec-butyllithium having a concentration of 1.3 M were added thereto. The resulting solution was added with 65 g of butadiene at 18 ° C. and polymerized for 5 hours to obtain a living anion of polybutadiene.
As a result of collecting a sample from the obtained reaction mixture and measuring by GPC, the resulting polybutadiene has a polystyrene-equivalent number average molecular weight (Mn) of 29,400 and a molecular weight distribution (Mw / Mn) of 1.01. I found out.
(2) The reaction mixture obtained in (1) above was cooled to −3 ° C., and to this was added isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.8M. A mixed solution prepared from 20 ml of toluene solution and 6 ml of 1,2-dimethoxyethane was added and stirred for 10 minutes. Further, to this solution was added a mixed solution prepared from 3 g of a toluene solution of 65 g of methyl methacrylate and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.8 M, and the mixture was heated to 0 ° C. For 2 hours.
A sample was taken from the obtained reaction mixture and measured by GPC. As a result, the number average molecular weight (Mn) in terms of polystyrene was 49,300 and the molecular weight distribution (Mw / Mn) was 1.03. It turned out to be. Moreover, the peak derived from the polybutadiene (homopolymer) obtained in (1) above is not observed, and the polymer produced is only butadiene-methyl methacrylate diblock copolymer (PBd-b-PMMA). I understood. In addition, the sample ¹ As a result of H-MNR analysis, the weight ratio of polybutadiene block / polymethyl methacrylate block in the obtained polymer was 47/53, and the ratio (molar ratio) of 1,4 bonds / 1,2 bonds in the polybutadiene block was as follows. It was found to be 10/90.
[0127]
Reference example 1
This reference example is a production example of a block copolymer obtained by converting a polybutadiene block into a substantial ethylene-butylene copolymer block by hydrogenating the block copolymer obtained in Example 9.
This was reacted with a nickel / aluminum-based hydrogenation catalyst (nickel content: 1 mmol; aluminum content: 3 mmol), and this was added to the reaction mixture finally obtained in Example 9. The resulting mixture was heated to 80 ° C. with stirring in a hydrogen-pressurized (1 MPa) atmosphere, and reacted at this temperature for 3 hours. During this time, hydrogen pressure was maintained at 1 MPa by supplying hydrogen.
Of the resulting reaction mixture ¹ As a result of H-MNR analysis, 98% of the double bonds of the polybutadiene block disappeared in the produced polymer, and a diblock copolymer (hydrogenated PBd having a hydrogenated polybutadiene block and a polymethyl methacrylate block). -B-PMMA) was found to be obtained.
[0128]
Example 10 (Synthesis example of isoprene-n-butyl acrylate diblock copolymer) This example is a polyisoprene obtained by addition reaction (polymerization) of a large amount of isoprene to sec-butyllithium (organic alkali metal compound). Of a living anion (polyisoprenyl lithium; polymerization initiator compound) and acrylic acid n in the presence of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum (organoaluminum compound) This is a production example of an isoprene-n-butyl acrylate diblock copolymer comprising a polymerization process of butyl.
(1) The inside of a 1 liter autoclave was purged with nitrogen, and 440 g of toluene and 2.8 ml of a cyclohexane solution of sec-butyllithium having a concentration of 1.3 M were added thereto. A polyisoprene living anion was obtained by adding 55 g of isoprene at 23 ° C. to the obtained solution and polymerizing for 4 hours.
As a result of collecting a sample from the obtained reaction mixture and measuring by GPC, the resulting polyisoprene has a polystyrene-equivalent number average molecular weight (Mn) of 11,000 and a molecular weight distribution (Mw / Mn) of 1.02. It turns out that there is.
(2) The reaction mixture obtained in the above (1) was cooled to −31 ° C., and to this was added isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.8M. A mixed solution prepared from 40 ml of a toluene solution and 7 ml of 1,2-dimethoxyethane was added and stirred for 10 minutes. Further, to this solution was added a mixed solution prepared from 5 g of a toluene solution of 55 g of n-butyl acrylate and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum having a concentration of 0.8 M, and − Polymerization was carried out at 27 ° C. for 2 hours.
Sampling was taken from the obtained reaction mixture and measured by GPC. As a result, the number average molecular weight (Mn) in terms of polystyrene was 37,800 and the molecular weight distribution (Mw / Mn) was 1.03. It turned out to be. In addition, no peak derived from the polyisoprene (homopolymer) obtained in (1) above was observed, and the only polymer produced was isoprene-n-butyl acrylate diblock copolymer (PIp-b-PnBA). It turned out to be. In addition, the sample ¹ As a result of H-MNR analysis, the weight ratio of polyisoprene block / poly (n-butyl acrylate) block in the obtained polymer was 49/51, and the ratio of 1,4 bonds / 3,4 bonds in the polyisoprene block ( The molar ratio was found to be 7/93.
About the obtained isoprene-acrylic acid n-butyl diblock copolymer and the polyisoprene obtained by said (1), a GPC chart is accumulated and shown in FIG. In FIG. 1, curve A and curve B indicate isoprene-n-butyl acrylate diblock copolymer and polyisoprene, respectively.
[0129]
From the above Examples 9 and 10, according to the production method of the present invention, a block copolymer having a diene polymer block and a (meth) acrylic ester polymer block has a narrow molecular weight distribution and an extremely high block efficiency. It can be seen that it can be manufactured.
[0130]
【The invention's effect】
According to the present invention, for a wide range of (meth) acrylic acid esters such as methyl methacrylate, tert-butyl methacrylate, and n-butyl acrylate, an organic alkali metal compound having relatively good convenience such as sec-butyl lithium. Is used for anionic polymerization with high initiation efficiency and high living property in a solvent that is easy to recover and reuse, such as a hydrocarbon solvent, under a moderate cooling condition such as −30 ° C. to 15 ° C. It becomes possible. Therefore, according to the present invention, a (meth) acrylic acid ester polymer such as a block copolymer can be industrially advantageously produced.
[Brief description of the drawings]
FIG. 1 shows a GPC chart (A) of an isoprene-n-butyl acrylate diblock copolymer finally obtained in Example 10 according to the present invention and a method for producing the diblock copolymer. It is a GPC chart (B) of the polyisoprene prepared in the first step. The horizontal axis represents the outflow time.

Claims (10)

When anionic polymerization of methacrylic acid ester or acrylic acid ester using a polymerization initiator compound, as the polymerization initiator compound, a conjugated diene compound selected from 1,3-butadiene and isoprene , polystyryl lithium, poly-α- An addition reaction product with an organic alkali metal compound selected from methyl styryl lithium and butyl lithium is used, and is represented by the formula: Al—O—Ar (wherein Ar represents an aromatic ring) in the polymerization system. A polymerization method comprising the presence of a tertiary organoaluminum compound containing a chemical structure in the molecule.   The polymerization method according to claim 1, wherein the methacrylic acid ester or acrylic acid ester is an ester of a primary alcohol and methacrylic acid or acrylic acid.   The polymerization method according to claim 1 or 2, wherein the conjugated diene compound is 1,3-butadiene. The polymerization process according to any one of claims 1 to 3 organic alkali metal compound is sec- butyl lithium. The polymerization process according to any one of claims 1 to 3 organic alkali metal compound is polystyryl lithium.   The tertiary organoaluminum compound has a chemical structure in which two or more of the three bonds of the aluminum atom are bonded to an aromatic ring through an oxygen atom. Polymerization method.   The polymerization method according to any one of claims 1 to 6, wherein at least a part of the tertiary organoaluminum compound is mixed into a methacrylic acid ester or an acrylic acid ester and then added to the polymerization system.   The polymerization method according to any one of claims 1 to 7, further comprising an ether compound or a tertiary polyamine compound in the polymerization system.   A method for producing a polymer comprising polymerizing a methacrylic acid ester or an acrylic acid ester by the polymerization method according to any one of claims 1 to 8.   A process for producing a block copolymer comprising polymerizing a methacrylic acid ester or an acrylic acid ester by the polymerization method according to claim 5.

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