JP4349018B2 - Method for producing amino group-containing polymer particles - Google Patents

Description

[式中、Ｒ１は水素原子またはメチル基、Ｒ２〜Ｒ４はメチル基を表す。ｎは１以上の整数を表す。]
＜２＞ 前記反応において、一般式（Ｉ）で表される（メタ）アクリレート重合体を有する架橋ポリマー粒子を膨潤させうる非反応性溶媒を用いることを特徴とする上記＜１＞に記載のアミノ基含有ポリマー粒子の製造方法。
＜３＞ 前記アミン類化合物がジエチレントリアミン及び１，６−ジアミノヘキサンから選択される１種以上であることを特徴とする上記＜１＞または＜２＞に記載のアミノ基含有ポリマー粒子の製造方法。
＜４＞ 前記非反応性溶媒が、メシチレンであることを特徴とする上記＜２＞または＜３＞に記載のアミノ基含有ポリマー粒子の製造方法。
＜５＞ 前記チタニウムテトラアルコキシドが、テトラ−ｎ−プロポキシチタンであることを特徴とする上記＜１＞〜＜４＞のいずれか１項に記載のアミノ基含有ポリマー粒子の製造方法。
【００１３】
【発明の実施の形態】
本発明のアミノ基含有ポリマー粒子の製造方法は、（メタ）アクリレート重合体を有する架橋ポリマー粒子を、含金属エステル交換反応用触媒であるチタニウムテトラアルコキシドの存在下、少なくとも２個の一級アミノ基を有するアミン類化合物とを反応させることを特徴とする。
【００１４】
ここで「（メタ）アクリレート」とは、常用されるように「アクリル酸エステル」および「メタクリル酸エステル」を意味する。
本発明の製造方法により、特殊な原料や反応性官能基を有する単量体を必要としない安価で、安全性が高く、複雑な操作を必要とすることなく、アミノ基量の制御が容易で、しかも粒子物性に悪影響を与える官能基の残存がないアミノ基含有ポリマー粒子を提供することができる。
【００１５】
以下、本発明を具体的に説明する。
【００１６】
＜架橋ポリマー粒子＞
本発明に用いられる架橋ポリマー粒子は、下記一般式（Ｉ）で表される（メタ）アクリレート重合体を構成成分として有する。
【００１７】
【化３】

式中、Ｒ１は水素原子またはメチル基、Ｒ２〜Ｒ４は、メチル基を表す。ｎは１以上の整数を表す。
【００２１】
前記一般式（Ｉ）で表される（メタ）アクリレート重合体の具体例としては、ｔ−ブチル（メタ）アクリレートが挙げられる。ｔ−ブチル（メタ）アクリレートの重合体が、その単量体の入手性、価格、反応性の点で好ましい。
【００２２】
本発明の架橋ポリマー粒子は、具体的には、前記単量体と、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、グリシジル（メタ）アクリレート、２−（［１'−メチルプロピリデンアミノ］カルボキシアミノ）エチル（メタ）アクリレート等の架橋性を有する単量体とを共重合することによって得られ、重合時に架橋構造とするか、重合によるポリマー粒子化した後に架橋させてもよい。
【００２３】
また、前記架橋ポリマー粒子は、上記単量体の重合体成分の他に、他の単量体を共重合させても得ることができる。その重合体がエステル交換能力がないかあっても弱い単量体を、上記単量体と共重合させ、その共重合比を変えることで粒子のアミノ基を制御することができる。この目的に好適な前記他の単量体としては、スチレン、メチル（メタ）アクリレート等が挙げられる。
【００２４】
さらに架橋ポリマー粒子の着色を目的に、公知の染料、顔料、カーボンブラック、磁性粉などを添加することも可能である。
また、前記単量体とともに、トルエン、オクタン、シクロヘキサノン、ジブチルフタレート、ラウリルアルコール等の非重合性の添加剤を入れ、重合後に抽出除去して粒子を多孔質とすることも可能である。
【００２５】
本発明のアミノ基含有架橋ポリマー粒子は、特殊な反応性官能基を有さないので添加剤や溶媒との反応、残存による粒子物性への悪影響が全くないか、きわめて少ないという利点がある。
【００２６】
＜アミン類化合物＞
本発明におけるアミン類化合物とは、一分子の中に少なくとも２個の一級アミノ基を有する化合物である。但し、水酸基を含まないものとする。
【００２７】
それらの具体例としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、１，６−ジアミノヘキサン、１，７−ヘプタンジアミン、１，１０−ジアミノデカン、１，３−ビス（アミノメチル）シクロヘキサン、ビス（３−アミノプロピル）アミン、４，４’−ジアミノジシクロヘキシルメタン、４，７，１０−トリオキサ−１，１３−トリデカンジアミン、４，９−ジオキサ−１，１２−ドデカンジアミン、ｍ−キシリレンジアミン、１，３−ジアミノ−２−ヒドロキシプロパン、ポリオキシエチレンビスアミン、ジェファーミンとして知られるポリオキシアルキレンアミン等が挙げられる。また、一級アミノ基を側鎖に有するアミノオリゴマー、アミノポリマーであってもよい。アミノオリゴマー及びアミノポリマーは、ポリビニルアミンとして三菱化学（株）の商品カタログ等に記載されているものを用いることができる。
【００２８】
本発明では、上記アミン類化合物の一級アミノ基が、前述の（メタ）アクリル重合体のエステル部とエステル交換することによりポリマー粒子と結合し、他端のアミノ基が残りアミノ基含有ポリマー粒子となるのである。該エステル交換をスムーズに進行させるため、該ポリマー粒子に含まれる該官能基の総モル量に対し等量以上のアミン類化合物を反応させることが好ましいが、実際にはポリマー粒子中の全ての官能基がエステル交換するわけではないので等量以下であってもかまわない。
また、使用するアミン類化合物の量を調整することにより、アミノ基含有量の調整をすることができる。
【００２９】
＜含金属エステル交換反応用触媒＞
本発明で添加する含金属エステル交換反応用触媒は、ポリエステル合成時に使用される、いわゆるエステル交換触媒である。
例えば、酢酸鉛、酢酸亜鉛、アセチルアセトネート亜鉛、酢酸カドニウム、酢酸マンガン、マンガンアセチルアセトネート、酢酸コバルト、コバルトアセチルアセトネート、酢酸ニッケル、ニッケルアセチルアセトネート、酢酸ジルコニウム、ジルコニウムアセチルアセトネート、ジルコニウムテトラ−ｎ−ブトキシド、酢酸チタン、テトラブトキシチタネート、テトライソプロポキシチタネート、チタニウムオキシアセチルアセトネート、酢酸鉄、アセチルアセトネート鉄、酢酸ニオブなどの遷移金属化合物、ジブチルスズオキシド、モノブチルヒドロキシスズオキサイド、ジブチルスズジラウレート、三酸化アンチモン、酸化ゲルマニウム、炭酸ビスマスオキシド、酢酸ビスマスオキシドなどの典型金属化合物があげられる。
また、酢酸マグネシウム、酢酸リチウム、酢酸カルシウム、酢酸カリウム、炭酸カリウム，炭酸セシウムなどのアルカリ金属化合物またはアルカリ土類金属化合物、さらに、酢酸ランタン、酢酸サマリウム、酢酸ユウロピウム、酢酸エルビウム、酢酸イッテルビウムなどの希土類化合物も用いることができる。
【００３０】
これらの触媒は、単独で用いても、２種以上組合せて用いてもよい。この中でも、本発明においては、溶媒への溶解性、反応性の点でより好ましいチタニウムテトラアルコキシドを用いる。チタニウムテトラアルコキシドとしては、例えば、テトラ−ｎ−プロポキシチタン、テトライソプロポキシチタン、テトラ−ｎ−ブトキシチタン、テトライソブトキシチタン、テトラ−ｔ−ブトキシチタン、テトラ−第二−ブトキシチタン、テトラ−ｎ−アミルオキシチタン、トリイソアミルオキシイソプロポキシチタンなどが挙げられる。
【００３１】
前記架橋ポリマー粒子に対する触媒の添加量（含有量）は、粒子総重量１００質量部に対して、通常０．０１〜５０質量部が用いられる。好ましくは０．１〜２０質量部、さらに好ましくは０．５〜１０質量部である。
触媒を０．０１〜５０質量部の範囲とすることにより、アミノ基が導入し易くなり、また、反応後の触媒の除去も有利に進行させることができる。
【００３２】
本発明において、架橋ポリマー粒子を得る粒子化には公知の方法が利用でき、例えば、懸濁重合法、乳化重合法、分散重合法、シード重合法等が好適に用いられる。さらに、膜乳化法として知られる乳化方法を使って懸濁重合することもできる。
【００３３】
前記重合には、必要に応じて、当業者には周知の重合開始触媒を用いることができる。
具体的には、ジアシルパーオキサイド、ケトンパーオキサイドおよびアルキルハイドロパーオキサイドのような有機過酸化物；過酸化水素およびオゾンのような無機過酸化物；およびアゾビスバレロニトリル（ＡＩＢＮ；和光純薬社よりＶ−６０として入手可能）、２，２’−アゾビス（２−メチルブチロニトリル）（和光純薬社よりＶ−５９として入手可能）および２，２’−アゾビス（２，４−ジメチルバレロニトリル）（和光純薬社よりＶ−６５として入手可能）のような油溶性アゾ系有機化合物；２，２’−アゾビス（２−アミジノプロパン）二酸塩（和光純薬社よりＶ−５０として入手可能）、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］（和光純薬社よりＶＡ−０８６として入手可能）および２，２’−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］二酸塩（和光純薬社よりＶＡ−０４４として入手可能）のような水溶性アゾ系有機化合物が挙げられる。重合開始剤を用いる場合は、それらは重合が良好に開始されるのに充分な量で用いられる。このような量は当業者に周知である。一般には、０．１〜５．０質量％の量で用いることが好ましい。
【００３４】
架橋ポリマー粒子の架橋度が高い場合には、反応促進の目的でポリマー粒子を膨潤させうる非反応性溶媒を助溶剤として添加することが好ましい。例えば、キシレン、メシチレン、ジエチルベンゼン、シクロヘキシルベンゼン、ジメチルナフタレン、シメン、ジメトキシベンゼンなどの芳香族化合物、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル、ジフェニルエーテル、ジベンジルエーエル、フェネトール、ブチルフェニルエーテルなどのエーテル化合物、アセトフェノン、イソホロン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノンなどのケトン化合物、ジクロロベンゼン、クロロトルエン、ジクロロトルエンなどのハロゲン化合物があげられるが、前記目的を達成する非反応性溶媒であればいずれでも使用できる。この中でも、特に、キシレン、メシチレン、ジメトキシベンゼンなどの芳香族化合物が反応性の点で好ましい。
【００３５】
本発明において、架橋ポリマー粒子と、アミン類化合物との反応割合は、架橋ポリマー粒子のエステル部の組み合わせ及びこれら官能基の導入量により異なるが、基本的には架橋ポリマー粒子の重量で約２倍から１０倍量の上記アミン類化合物を用い、必要に応じて用いられる上記非反応性溶媒中、１２０℃から２００℃の反応条件で、５〜２４時間程度加熱して反応させることにより、アミノ基含有架橋ポリマー粒子を得ることができる。これらの添加量を調節することによって、容易にアミノ基量の制御が可能である。
【００３６】
ここで、アミノ基導入量の再現性の面で、あらかじめ反応前に粒子を分級処理し、粒径をそろえてから反応させることが望ましい。こうして得られたアミノ基含有架橋ポリマー粒子は、メタノール等の溶媒に希釈分散させ、濾別し、更に水洗及び／又は溶剤洗浄の後、噴霧乾燥、減圧乾燥、凍結乾燥等の通常の手段によって粉体として単離することができる。
【００３７】
また、大気下のみならず、加圧下においても、反応させることができるが、これらのその他の反応条件は、必要に応じて適用されるもので、特に限定されるものでははい。
【００３８】
前記操作により得られたアミノ基含有架橋ポリマー粒子におけるアミノ基量は、一般的な滴定法により求めることができる。
例えば、架橋ポリマーの一定量に過塩素酸、酢酸溶媒等の試薬を一定量加え、ＲＴで１時間攪拌し、遠心分離機等により粒子と上澄みを分離し、上澄みを自動滴定装置等を用いて滴定することにより、そのアミノ基量を求めることができる。
【００３９】
本発明の製造方法により得られたアミノ基含有架橋ポリマー粒子は、診断薬および医薬品担体、クロマトグラフィ担体、粘性調整剤、樹脂成形材料、塗料添加剤、架橋／硬化剤および化粧品添加剤のような用途に好適に使用可能である。
【００４０】
【実施例】
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例中、部は質量部を示す。
【００４１】
（参考例１）（架橋ポリマー粒子の合成）
ｔ−ブチルメタクリレート（和光純薬（株）製）１００部、ジビニルベンゼン（純度５５％）５部を用いて懸濁重合を行い、分級操作を施し平均粒径１５μｍの架橋ポリマー粒子を得た。得られた粒子をイオン交換水及び溶剤で洗浄後、単離乾燥して架橋ポリマー粒子を得た。
【００４２】
（参考例２）（比較用架橋ポリマー粒子の合成）
メチルメタクリレート（東京化成（株）製）７０部、ジビニルベンゼン（純度５５％）５部を用いて懸濁重合を行い、分級操作を施し平均粒径１５μｍの架橋ポリマー粒子を得た。得られた粒子をイオン交換水及び溶剤で洗浄後、単離乾燥して架橋ポリマー粒子を得た。
【００４３】
（実施例１）
参考例１で得られた架橋ポリマー粒子１０部をジエチレントリアミン（和光純薬（株）製）５０部に分散させ、メシチレン（和光純薬（株）製）１５部を加え、窒素雰囲気下テトラ−ｎ−プロポキシチタン（和光純薬（株）製）を０．２部滴下し、１４時間還流下反応させた。得られた微粒子をメタノールに分散／洗浄しさらにイオン交換水及び溶剤で洗浄後、単離乾燥してアミノ基含有ポリマー粒子を得た。このようにして得られたアミノ基含有ポリマー粒子の全アミノ基量を以下の方法で測定した。
【００４４】
上記粒子をキャップ付き試験管に秤量し、０．１Ｍ過塩素酸、酢酸溶媒（和光純薬（株）製）を一定量加え、室温で１時間攪拌した。反応液を３０００ｒｐｍで５分間遠心分離して粒子と上澄みに分けた。粒子をさらに酢酸（和光純薬（株）製）で超音波分散と遠心分離を繰り返し洗浄し、上澄みと洗浄液とをビーカーに集め、自動滴定装置（京都電子工業（株）製 ＡＴ−４１０）を用いて０．１Ｍ酢酸ナトリウム、酢酸溶媒（関東化学（株）製）で滴定した。粒子を加えないブランク実験も同時に行い、滴下量の差分から下式に従ってアミノ基量（Ａｍｍｏｌ／ｇ）を算出した。
Ａ＝（（Ｂ−Ｃ）×０．１×ｆ）／ｗ
ここで、Ｂはブランク実験での滴下量（ｍｌ）、Ｃはサンプルの滴下量（ｍｌ）、ｆは酢酸ナトリウム、酢酸溶媒のファクター、ｗは粒子の重量（ｇ）である。この粒子のアミノ基量は２．１ｍｍｏｌ／ｇであった。
【００４５】
（実施例２）
参考例１で得られた架橋ポリマー粒子１０部を１，６−ジアミノヘキサン（和光純薬（株）製）５０部に分散させ、窒素雰囲気下テトラ−ｎ−プロポキシチタン（和光純薬（株）製）０．２部を加えて、１４時間１７０℃で反応させた。得られた粒子をメタノールに分散／洗浄しさらにイオン交換水及び溶剤で洗浄後、単離乾燥してアミノ基含有ポリマー粒子を得た。このようにして得られたアミノ基含有ポリマー粒子のアミノ基量を実施例１と同じ方法で測定を行ったところ、この粒子のアミノ基量は１．２ｍｍｏｌ／ｇであった。
【００４６】
（比較例１）
実施例１で触媒を入れない以外は全く同じ処理を参考例１で得られた架橋重合微粒子に行い比較の粒子を得た。この粒子のアミノ基量を実施例１と同じ方法で測定を行ったところ、アミノ基は全く測定されなかった。
【００４７】
（比較例２）
実施例１と全く同じ処理を参考例２で得られた架橋ポリマー粒子に行い比較の粒子を得た。この粒子のアミノ基量を実施例１と同じ方法で測定を行ったところ、アミノ基は全く測定されなかった。
【００４８】
【発明の効果】
本発明によれば、特殊な原料や反応性官能基を有する単量体を必要としない安価で、安全性が高く、複雑な操作を必要とすることなく、アミノ基量の制御が容易で、しかも粒子物性に悪影響を与える官能基の残存がないアミノ基含有粒子の製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to crosslinked polymer particles having amino groups that can be suitably used for applications such as diagnostic agents and pharmaceutical carriers, chromatography carriers, viscosity modifiers, resin molding materials, paint additives, crosslinking / curing agents and cosmetic additives. It relates to the manufacturing method.
[0002]
[Prior art]
Functional polymers such as ion exchange resins and chelate resins have been widely used as carriers for various chemical substances. Such a functional polymer has various reactive groups on the surface of an insoluble polymer. Conventionally, functional polymers into which various active hydrogen-containing groups such as carboxyl groups, hydroxyl groups, and primary and secondary amino groups have been introduced have been used for various applications.
[0003]
In recent years, attempts have been made to fix physiologically active substances such as drugs and enzymes to functional polymers and deliver them to lesions. In such applications, the functional polymer carrier must carry the desired amount of drug uniformly and reliably. It is also necessary to have good dispersibility in various solvents. In general, when a functional polymer is used as a carrier such as a chemical, it has a variety of abundant reactivity and has primary and secondary amino groups that form stable bonds with various functional groups. It is preferable to use it. Amino group-containing polymer particles having good supportability are also suitable as chromatographic carriers, viscosity modifiers, resin molding materials, paint additives, crosslinking / curing agents, and cosmetic additives in addition to the above-mentioned use as pharmaceutical carriers. Since it can be used for, demand is increasing.
[0004]
Conventionally, as a method of producing polymer particles having an amino group, a monomer having an amino group is previously suspension-polymerized in an aqueous medium to form particles, or a crosslinked polymer particle having a reactive functional group is produced, There is a method of introducing an amino group into a particle by reacting with an amino group-containing compound that reacts with the reactive functional group and binds to the particle.
[0005]
As an example of the former, an ethylenically unsaturated amine polymer is prepared by previously reacting an amine polymer having at least two primary amino groups with a specific vinyl monomer that reacts with the amino group. Although a method for obtaining a skeleton-forming ethylenically unsaturated monomer by suspension copolymerization in an aqueous medium has been shown (see, for example, Patent Document 1), ethylenically unsaturated amine polymers are industrially mass-produced. Therefore, it must be carried out from the production of the raw material ethylenically unsaturated amine polymer, and the operation is complicated. In addition, since ethylenically unsaturated amine polymers are polymers, they cannot be distilled or recrystallized and are difficult to purify. To increase the purity, reprecipitation and refining must be repeated, leading to an increase in cost. . Further, the specific vinyl monomer used as a raw material is a reactive monomer such as a glycidyl group-containing ethylenically unsaturated monomer, an isocyanate ester-based ethylenically unsaturated monomer, or a vinyl group-containing organic chloride compound. In general, sex monomers are toxic and unfavorable for safety and health, and have poor storage stability.
[0006]
As an example of the latter, a method for producing a crosslinked fine particle having an amino group by reacting a crosslinked fine particle having a glycidyl group with a compound having two or more amino groups is described (for example, see Patent Document 2). However, reactive functional groups such as glycidyl groups are liable to cause side reactions during polymerization, making it difficult to control the amount of amino groups, and glycidyl groups are highly reactive with amino groups. Considering the mechanism, it is difficult to control the amount of amino groups and the degree of crosslinking at the same time. Furthermore, the meth (acrylic acid) ester having a glycidyl group is highly toxic as described above, and is not preferable for safety and health.
[0007]
In addition, an amino group introduction method by reacting an epoxy group (for example, glycidyl group) and a crosslinked polymer fine particle having a carboxyl group with ethylenediamine or the like is disclosed. However, a carboxyl group and an amine compound such as ethylenediamine form a salt structure rather than a covalent bond, so that there is a problem of desorption at a pH in an aqueous medium. Moreover, about an epoxy group (for example, glycidyl group), there exists a problem similar to the said glycidyl group.
[0008]
Thus, the conventional manufacturing method for obtaining the polymer particle containing an amino group has a subject.
[0009]
[Patent Document 1]
Japanese Patent Laid-Open No. 5-170845 [Patent Document 2]
JP-A-5-216049 [Patent Document 3]
JP-A-5-188384 [0010]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to provide an inexpensive, highly safe, and complicated operation that does not require a special raw material or a monomer having a reactive functional group as found in the conventional production method of amino group-containing particles. It is an object of the present invention to provide a method for producing amino group-containing polymer particles that can easily control the amount of amino groups and that does not have functional groups that adversely affect particle physical properties.
[0011]
[Means for Solving the Problems]
That is, the present invention
<1> The crosslinked polymer particles having represented (meth) acrylate polymer by the following formula (I), the presence of titanium tetraalkoxide, amine compounds you have at least two primary amino groups and reaction A process for producing amino group-containing polymer particles, characterized by comprising:
[0012]
[Chemical formula 2]

[Wherein R1 represents a hydrogen atom or a methyl group, and R2 to R4 each represents a methyl group. n represents an integer of 1 or more. ]
<2> The amino according to <1>, wherein a non-reactive solvent capable of swelling the crosslinked polymer particles having the (meth) acrylate polymer represented by the general formula (I) is used in the reaction. A method for producing group-containing polymer particles.
<3> The method for producing amino group-containing polymer particles according to <1> or <2>, wherein the amine compound is at least one selected from diethylenetriamine and 1,6-diaminohexane .
<4> The method for producing amino group-containing polymer particles according to <2> or <3>, wherein the non-reactive solvent is mesitylene.
<5> The method for producing amino group-containing polymer particles according to any one of <1> to <4>, wherein the titanium tetraalkoxide is tetra-n-propoxytitanium.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing amino group-containing polymer particles of the present invention, crosslinked polymer particles having a (meth) acrylate polymer are converted into at least two primary amino groups in the presence of titanium tetraalkoxide which is a metal-containing transesterification catalyst. and to that amine compound perforated and wherein the reacting.
[0014]
Here, “(meth) acrylate” means “acrylic acid ester” and “methacrylic acid ester” as commonly used.
The production method of the present invention is inexpensive, does not require a special raw material or a monomer having a reactive functional group, is highly safe, and can easily control the amount of amino groups without requiring complicated operations. In addition, it is possible to provide amino group-containing polymer particles that do not have residual functional groups that adversely affect the physical properties of the particles.
[0015]
Hereinafter, the present invention will be specifically described.
[0016]
<Crosslinked polymer particles>
The crosslinked polymer particles used in the present invention have a (meth) acrylate polymer represented by the following general formula (I) as a constituent component.
[0017]
[Chemical 3]

In the formula, R1 represents a hydrogen atom or a methyl group, and R2 to R4 represent a methyl group. n represents an integer of 1 or more.
[0021]
Specific examples of the above formula (I) (meth) acrylate polymers include t- butyl (meth) acrylate and. A polymer of t -butyl (meth) acrylate is preferable from the viewpoint of availability, cost, and reactivity of the monomer.
[0022]
Specifically, the crosslinked polymer particles of the present invention include the monomer, divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, 2-([1′- It is obtained by copolymerizing with a monomer having crosslinkability such as methylpropylideneamino] carboxyamino) ethyl (meth) acrylate, and is made into a crosslinked structure at the time of polymerization, or crosslinked after polymerization into polymer particles. Also good.
[0023]
The crosslinked polymer particles can also be obtained by copolymerizing other monomers in addition to the polymer component of the monomers. Even if the polymer has no transesterification ability, the amino group of the particles can be controlled by copolymerizing a weak monomer with the monomer and changing the copolymerization ratio. Examples of the other monomer suitable for this purpose include styrene and methyl (meth) acrylate.
[0024]
Furthermore, for the purpose of coloring the crosslinked polymer particles, known dyes, pigments, carbon black, magnetic powder and the like can be added.
In addition to the monomer, non-polymerizable additives such as toluene, octane, cyclohexanone, dibutyl phthalate, and lauryl alcohol can be added and extracted and removed after polymerization to make the particles porous.
[0025]
Since the amino group-containing crosslinked polymer particles of the present invention do not have a special reactive functional group, there is an advantage that there is no or very little adverse effect on the physical properties of the particles due to the reaction with additives and solvents and the residual.
[0026]
<Amine compounds>
The amine compound in the present invention is a compound you have at least two primary amino groups in one molecule. However, it shall not contain a hydroxyl group.
[0027]
Specific examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, 1,6-diaminohexane, 1,7-heptanediamine, 1,10-diaminodecane, 1,3-bis (aminomethyl) cyclohexane, bis (3 -Aminopropyl) amine, 4,4'-diaminodicyclohexylmethane, 4,7,10-trioxa-1,13-tridecanediamine, 4,9-dioxa-1,12-dodecanediamine, m-xylylenediamine, Examples include 1,3-diamino-2-hydroxypropane, polyoxyethylene bisamine, and polyoxyalkyleneamine known as Jeffamine. Moreover, the amino oligomer and amino polymer which have a primary amino group in a side chain may be sufficient. As the amino oligomer and amino polymer, those described in the product catalog of Mitsubishi Chemical Corporation as polyvinylamine can be used.
[0028]
In the present invention, the primary amino group of the amine compound binds to the polymer particle by transesterification with the ester portion of the (meth) acrylic polymer, and the amino group at the other end remains as the amino group-containing polymer particle. It becomes. In order to facilitate the transesterification, it is preferable to react an equal amount or more of an amine compound with respect to the total molar amount of the functional group contained in the polymer particle. Since the group does not transesterify, the amount may be equal or less.
Further, the amino group content can be adjusted by adjusting the amount of the amine compound used.
[0029]
<Metal-containing transesterification catalyst>
Metal-containing transesterification reaction catalyst to be added in the present invention is used during the polyester synthesis, so-called transesterification catalyst.
For example, lead acetate, zinc acetate, zinc acetylacetonate, cadmium acetate, manganese acetate, manganese acetylacetonate, cobalt acetate, cobalt acetylacetonate, nickel acetate, nickel acetylacetonate, zirconium acetate, zirconium acetylacetonate, zirconium tetra -Transition metal compounds such as n-butoxide, titanium acetate, tetrabutoxy titanate, tetraisopropoxy titanate, titanium oxyacetylacetonate, iron acetate, iron acetylacetonate, niobium acetate, dibutyltin oxide, monobutylhydroxytin oxide, dibutyltin dilaurate And typical metal compounds such as antimony trioxide, germanium oxide, bismuth carbonate, and bismuth acetate.
Also, alkali metal compounds or alkaline earth metal compounds such as magnesium acetate, lithium acetate, calcium acetate, potassium acetate, potassium carbonate, cesium carbonate, and rare earths such as lanthanum acetate, samarium acetate, europium acetate, erbium acetate, ytterbium acetate Compounds can also be used.
[0030]
These catalysts may be used alone or in combination of two or more. Among these, in the present invention, titanium tetraalkoxide, which is more preferable in terms of solubility in a solvent and reactivity, is used . Examples of the titanium tetraalkoxide include tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra-t-butoxy titanium, tetra-secondary butoxy titanium, and tetra-n. -Amyloxytitanium, triisoamyloxyisopropoxytitanium and the like.
[0031]
The added amount (content) of the catalyst to the crosslinked polymer particles is usually 0.01 to 50 parts by mass with respect to 100 parts by mass of the total particle weight. Preferably it is 0.1-20 mass parts, More preferably, it is 0.5-10 mass parts.
By making a catalyst into the range of 0.01-50 mass parts, an amino group becomes easy to introduce | transduce and the removal of the catalyst after reaction can also be advanced advantageously.
[0032]
In the present invention, a known method can be used for forming the crosslinked polymer particles, and for example, a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a seed polymerization method and the like are preferably used. Furthermore, suspension polymerization can be performed using an emulsification method known as a membrane emulsification method.
[0033]
For the polymerization, if necessary, a polymerization initiation catalyst known to those skilled in the art can be used.
Specifically, organic peroxides such as diacyl peroxide, ketone peroxide and alkyl hydroperoxide; inorganic peroxides such as hydrogen peroxide and ozone; and azobisvaleronitrile (AIBN; Wako Pure Chemical Industries, Ltd.) 2,2′-azobis (2-methylbutyronitrile) (available as V-59 from Wako Pure Chemical Industries, Ltd.) and 2,2′-azobis (2,4-dimethylvalero) Nitrile) (available from Wako Pure Chemical Industries, Ltd. as V-65); an oil-soluble azo organic compound; 2,2′-azobis (2-amidinopropane) dioic acid salt (V-50 from Wako Pure Chemical Industries, Ltd.) Available), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (available from Wako Pure Chemical Industries, Ltd. as VA-086) and Water-soluble azo organic compounds such as 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dioic acid salt (available as VA-044 from Wako Pure Chemical Industries, Ltd.) can be mentioned. If polymerization initiators are used, they are used in an amount sufficient to initiate polymerization well. Such amounts are well known to those skilled in the art. In general, it is preferably used in an amount of 0.1 to 5.0% by mass.
[0034]
When the degree of crosslinking of the crosslinked polymer particles is high, it is preferable to add a non-reactive solvent that can swell the polymer particles as a cosolvent for the purpose of promoting the reaction. For example, aromatic compounds such as xylene, mesitylene, diethylbenzene, cyclohexylbenzene, dimethylnaphthalene, cymene, dimethoxybenzene, ether compounds such as diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, acetophenone, isophorone And ketone compounds such as diisobutyl ketone, cyclohexanone and methylcyclohexanone, and halogen compounds such as dichlorobenzene, chlorotoluene and dichlorotoluene. Any non-reactive solvent which can achieve the above-mentioned purpose can be used. Among these, aromatic compounds such as xylene, mesitylene, and dimethoxybenzene are particularly preferable in terms of reactivity.
[0035]
In the present invention, the reaction ratio between the crosslinked polymer particles and the amine compound varies depending on the combination of the ester portion of the crosslinked polymer particles and the amount of these functional groups introduced, but is basically about twice the weight of the crosslinked polymer particles. 10 to 10 times the amount of the amine compound, and the amino group is reacted by heating for about 5 to 24 hours under the reaction conditions of 120 to 200 ° C. in the non-reactive solvent used as necessary. Containing crosslinked polymer particles can be obtained. By adjusting these addition amounts, the amount of amino groups can be easily controlled.
[0036]
Here, in terms of the reproducibility of the amino group introduction amount, it is desirable to classify the particles in advance before the reaction, and to react after aligning the particle diameters. The amino group-containing crosslinked polymer particles thus obtained are diluted and dispersed in a solvent such as methanol, filtered, and further washed with water and / or solvent, and then powdered by ordinary means such as spray drying, reduced pressure drying, freeze drying and the like. It can be isolated as a body.
[0037]
Further, the reaction can be carried out not only in the air but also under pressure, but these other reaction conditions are applied as required and are not particularly limited.
[0038]
The amount of amino groups in the amino group-containing crosslinked polymer particles obtained by the above operation can be determined by a general titration method.
For example, a certain amount of a reagent such as perchloric acid or acetic acid solvent is added to a certain amount of the crosslinked polymer, stirred for 1 hour at RT, particles and supernatant are separated using a centrifuge, etc., and the supernatant is separated using an automatic titrator or the like. By titrating, the amount of the amino group can be determined.
[0039]
The amino group-containing crosslinked polymer particles obtained by the production method of the present invention are used for diagnostic agents and pharmaceutical carriers, chromatography carriers, viscosity modifiers, resin molding materials, paint additives, crosslinking / curing agents and cosmetic additives. Can be suitably used.
[0040]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, in an Example, a part shows a mass part.
[0041]
(Reference Example 1) (Synthesis of crosslinked polymer particles)
Suspension polymerization was performed using 100 parts of t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 parts of divinylbenzene (purity 55%), and classification operation was performed to obtain crosslinked polymer particles having an average particle diameter of 15 μm. The obtained particles were washed with ion exchange water and a solvent, and then isolated and dried to obtain crosslinked polymer particles.
[0042]
Reference Example 2 (Synthesis of Comparative Crosslinked Polymer Particles)
Suspension polymerization was performed using 70 parts of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of divinylbenzene (purity 55%), and classification operation was performed to obtain crosslinked polymer particles having an average particle diameter of 15 μm. The obtained particles were washed with ion exchange water and a solvent, and then isolated and dried to obtain crosslinked polymer particles.
[0043]
(Example 1)
10 parts of the crosslinked polymer particles obtained in Reference Example 1 are dispersed in 50 parts of diethylenetriamine (manufactured by Wako Pure Chemical Industries, Ltd.), 15 parts of mesitylene (manufactured by Wako Pure Chemical Industries, Ltd.) are added, and tetra-n is added under a nitrogen atmosphere. -Propoxy titanium (made by Wako Pure Chemical Industries, Ltd.) 0.2 part was dripped, and it was made to react under recirculation | reflux for 14 hours. The obtained fine particles were dispersed / washed in methanol, further washed with ion exchange water and a solvent, and then isolated and dried to obtain amino group-containing polymer particles. The total amino group content of the amino group-containing polymer particles thus obtained was measured by the following method.
[0044]
The above particles were weighed into a capped test tube, and fixed amounts of 0.1 M perchloric acid and acetic acid solvent (manufactured by Wako Pure Chemical Industries, Ltd.) were added, followed by stirring at room temperature for 1 hour. The reaction solution was centrifuged at 3000 rpm for 5 minutes and separated into particles and supernatant. The particles were further washed with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) by repeated ultrasonic dispersion and centrifugation, and the supernatant and washing solution were collected in a beaker, and an automatic titrator (AT-410, manufactured by Kyoto Electronics Industry Co., Ltd.) was used. The solution was titrated with 0.1 M sodium acetate and acetic acid solvent (manufactured by Kanto Chemical Co., Inc.). A blank experiment in which no particles were added was performed at the same time, and the amino group amount (Ammol / g) was calculated from the difference in the dripping amount according to the following formula.
A = ((BC) × 0.1 × f) / w
Here, B is a dripping amount (ml) in the blank experiment, C is a dripping amount (ml) of the sample, f is a factor of sodium acetate and acetic acid solvent, and w is a weight (g) of the particle. The amount of amino groups of the particles was 2.1 mmol / g.
[0045]
(Example 2)
10 parts of the crosslinked polymer particles obtained in Reference Example 1 are dispersed in 50 parts of 1,6-diaminohexane (manufactured by Wako Pure Chemical Industries, Ltd.), and tetra-n-propoxy titanium (Wako Pure Chemical Industries, Ltd.) under a nitrogen atmosphere. (Made) 0.2 part was added and it was made to react at 170 degreeC for 14 hours. The obtained particles were dispersed / washed in methanol, further washed with ion exchange water and a solvent, and then isolated and dried to obtain amino group-containing polymer particles. When the amino group content of the amino group-containing polymer particles thus obtained was measured by the same method as in Example 1, the amino group content of the particles was 1.2 mmol / g.
[0046]
(Comparative Example 1)
Except that the catalyst was not added in Example 1, the same treatment was performed on the crosslinked polymer fine particles obtained in Reference Example 1 to obtain comparative particles. When the amount of amino groups of the particles was measured by the same method as in Example 1, no amino groups were measured.
[0047]
(Comparative Example 2)
The same treatment as in Example 1 was performed on the crosslinked polymer particles obtained in Reference Example 2 to obtain comparative particles. When the amount of amino groups of the particles was measured by the same method as in Example 1, no amino groups were measured.
[0048]
【The invention's effect】
According to the present invention, it is inexpensive and does not require a special raw material or a monomer having a reactive functional group, is highly safe, and does not require complicated operations, and the amount of amino groups can be easily controlled. Moreover, it is possible to provide a method for producing amino group-containing particles having no residual functional groups that adversely affect particle physical properties.

Claims (5)

Represented by the following general formula (I) with (meth) crosslinked polymer particles having an acrylate polymer, the presence of titanium tetraalkoxide, that is reaction with an amine compound you have at least two primary amino groups A method for producing amino group-containing polymer particles.

[Wherein R1 represents a hydrogen atom or a methyl group, and R2 to R4 each represents a methyl group. n represents an integer of 1 or more. ]   The amino group-containing polymer particle according to claim 1, wherein a non-reactive solvent capable of swelling the crosslinked polymer particle having the (meth) acrylate polymer represented by the general formula (I) is used in the reaction. Manufacturing method. The method for producing amino group-containing polymer particles according to claim 1 or 2, wherein the amine compound is one or more selected from the following diethylenetriamine and 1,6-diaminohexane .

4. The method for producing amino group-containing polymer particles according to claim 2 or 3, wherein the non-reactive solvent is mesitylene. The method for producing amino group-containing polymer particles according to any one of claims 1 to 4, wherein the titanium tetraalkoxide is tetra-n-propoxytitanium.