JPS58174411A - Preparation of graft polymer of titanium oxide and polymeric compound - Google Patents
Preparation of graft polymer of titanium oxide and polymeric compoundInfo
- Publication number
- JPS58174411A JPS58174411A JP5945082A JP5945082A JPS58174411A JP S58174411 A JPS58174411 A JP S58174411A JP 5945082 A JP5945082 A JP 5945082A JP 5945082 A JP5945082 A JP 5945082A JP S58174411 A JPS58174411 A JP S58174411A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- monomer
- polymer
- reaction
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、チタン酸化物−高分子化合物グラフト重合体
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a titanium oxide-polymer compound graft polymer.
これまで、チタン酸化物の粒子は各種の顔料、添加剤お
よび誘電率の大きいことから電子回路用素子などへ応用
されているが、溶媒への分散性が一つのあい路となって
いた。そのために、Ｖランカップリング剤などの低分子
有機化合物をその表面に反応させる方法がとられている
が〔ポリマーダイジェスト、第３１巻、５７頁（１９７
９年）〕、高分子化合物を直接グラフト重合させ、グラ
フト重合が確認され上記の緒特性を改善させた例はない
。Until now, titanium oxide particles have been applied to various pigments, additives, and electronic circuit elements due to their high dielectric constant, but one of the obstacles has been their dispersibility in solvents. For this purpose, a method has been adopted in which a low-molecular organic compound such as a V-lan coupling agent is reacted on the surface [Polymer Digest, Vol. 31, p. 57 (197
9)], there has been no example of direct graft polymerization of a polymer compound, in which graft polymerization has been confirmed and the above-mentioned properties have been improved.
本発明者は、チタン酸化物に高分子化合物をグラフト重
合させ、実用上利用可能な溶媒良分散性のチタン酸化物
を得る目的で鋭意研究を重ねた結果、チタン酸化物をあ
らかじめ、アルキルリチウム塩と反応させて付加物を作
り、その付加物にエチレン誘導体モノマーを反応させる
と、その付加物を触媒としてその付加物表面より、グラ
フトポリマーが成長し、溶媒に良分散性のチタン酸化物
が生成することを見出した。本発明は、この知見に基づ
いてなされたものである。すなわち、本発明は、チタン
酸化物に生成する高分子に親和性のある溶媒中で、重合
前にアルキルリチウムで付加物を生成させ、その付加物
を本発明方法において用いるチタン酸化物とは酸化チタ
ンおよびブタン酸パリクム、チタン酸鉛などの酸化チタ
ンの変成塩の粉末をいうが、その大きさは小さいものは
制限ないが、大きいものは溶媒に懸濁可能なものであれ
ば、その制限はないが、通常１００ミクロン以下が望ま
しい。As a result of extensive research aimed at obtaining a practically usable titanium oxide with good dispersibility in solvents by graft polymerizing a polymer compound onto titanium oxide, the present inventor discovered that titanium oxide was preliminarily treated with an alkyl lithium salt. When reacting with ethylene derivative monomer, a graft polymer grows from the surface of the adduct using the adduct as a catalyst, producing titanium oxide with good dispersibility in the solvent. I found out what to do. The present invention has been made based on this knowledge. That is, in the present invention, an adduct is produced with alkyl lithium before polymerization in a solvent that has affinity for the polymer produced in titanium oxide, and the adduct is used in the method of the present invention. Refers to powders of modified salts of titanium and titanium oxide such as palicum butanoate and lead titanate.There is no restriction on the size of the powder, as long as it is small, but there is no restriction on the size of the powder as long as it can be suspended in a solvent. However, it is usually desirable to have a thickness of 100 microns or less.
本発明におけるアルキルリチウムのアルキル基は、メチ
ル、エチル、ｎ−プロピル、イソプロピル、ｎ−プテル
、イソブチルなどであり、アルキル基が極端に大きい場
合にはチタン酸化物表面の凹凸によってその反応が制限
される可能性もあり、低分子量アルキルリチウム具体的
にはｎ−ブチルリチウムが望ましい。また、アルキルリ
チウムは通常ベンゼン、トルエンなどの芳香族炭化水素
、ｎ−ヘキサン、シクロヘキサンなどの指環式化合物、
テトラヒドロフランなどのエーテル類の溶液として使用
する。The alkyl group of the alkyllithium in the present invention is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, etc. If the alkyl group is extremely large, the reaction may be limited by the unevenness of the titanium oxide surface. Therefore, low molecular weight alkyllithium, specifically n-butyllithium, is desirable. In addition, alkyl lithiums are usually aromatic hydrocarbons such as benzene and toluene, ring compounds such as n-hexane and cyclohexane,
Used as a solution in ethers such as tetrahydrofuran.
本発明に使用される重合性単量体とはＰｒ１ｃｅ −Ａ
ｌｆｒｅｙのＱ、ｅスキームでいうｅ値が正を示し、か
つＱ値が０．１以上であって具体的にはメタクリル酸メ
チル、メタクリル酸エチルなどのメタクリル酸アルキル
エステル、アクリル酸メチル、アクリル酸エチルなどの
アクリル酸アルキルエステル、およびアクリロニトリル
、メタクリロニトリルのことである。しかし、ｅ値が負
のスチレン等はチタン酸化物とアルキルリチウムによっ
て生成する付加物を開始点としてアニオン重合せず、本
発明の重合性単量体に含まれないが、上記のｅ値が正で
Ｑ値が０．１以上の単量体、と共に共重合するときには
使用することができる。The polymerizable monomer used in the present invention is Pr1ce-A
lfrey's Q, the e value in the e scheme is positive, and the Q value is 0.1 or more, specifically methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, methyl acrylate, and acrylic acid. Acrylic acid alkyl esters such as ethyl, acrylonitrile, and methacrylonitrile. However, styrene etc. with a negative e value do not undergo anionic polymerization using the adduct formed by titanium oxide and alkyl lithium as a starting point, and are not included in the polymerizable monomers of the present invention, but the above e value is positive. It can be used when copolymerizing with a monomer having a Q value of 0.1 or more.
本発明を実施するには重合体が溶解可能で重合反応を妨
げない有機溶剤の中から一つ選び、例えば芳香族炭化水
素、脂肪族炭化水素の中から一つを選び、その中でチタ
ン酸化物とアルキルリチウムとの反応を行なう。反応は
すべて不活性気体中で行ない、反応温度は特に制限はな
いが、５０℃から一２０℃の間が望ましい。この反応に
よってできる付加物にすぐに重合性単量体を加えて、引
き続いて不活性気体中で反応を行ない、チタン酸化物粒
子表面に重合性単量体をグラフトせしめる。反応停止は
通常のアニオン重合を禁止するものいずれでもよく、例
えばメ１：
タノールを加えて停止する。To carry out the present invention, one organic solvent is selected from among organic solvents in which the polymer can be dissolved and does not interfere with the polymerization reaction, for example, one is selected from aromatic hydrocarbons and aliphatic hydrocarbons, and titanium oxide is Reacts between substances and alkyl lithium. All reactions are carried out in an inert gas atmosphere, and the reaction temperature is not particularly limited, but is preferably between 50°C and -20°C. A polymerizable monomer is immediately added to the adduct produced by this reaction, followed by a reaction in an inert gas to graft the polymerizable monomer onto the surface of the titanium oxide particles. The reaction may be terminated by any method that inhibits normal anionic polymerization, for example, by adding methanol.
実施例 １
平均粒子径１０ミクロンの酸化チタン０．５を１００ｄ
のナス型フラスコに秤りとり、真空乾燥器で８０℃、２
４時間乾燥した。次いで、ト、ルエン２５−１を加え酸
化チタンを懸濁したのち、温度な０℃に保った。その後
１５％のｎ−ブチルリチウムへキチン溶液１ｄを加え６
０分間反応を行なうた。これらはすべて窒素気流中で行
なった。その反応終了後ただちにこの溶液に０．５２の
メタクリル酸メチルを加えマグネテックスターラーでか
きまぜながら６０分間重合を行なった。６０分後生量の
メチルアルコールを加え反応を終了させた。Example 1 100d of titanium oxide 0.5 with an average particle size of 10 microns
Weigh it into an eggplant-shaped flask and heat it in a vacuum dryer at 80℃ for 2 hours.
It was dried for 4 hours. Next, 25-1 of toluene was added to suspend titanium oxide, and the temperature was maintained at 0°C. Then add 1 d of chitin solution to 15% n-butyl lithium and add 6
The reaction was carried out for 0 minutes. All of this was done in a nitrogen stream. Immediately after the completion of the reaction, 0.52 methyl methacrylate was added to the solution and polymerization was carried out for 60 minutes while stirring with a magnetic stirrer. After 60 minutes, a fresh amount of methyl alcohol was added to terminate the reaction.
この反応物を３００ｗＩのメチルアルコールの中に移し
、出て来る沈殿物を集めて乾燥して重合収率とした。重
合率は５０％であった。またベンゼンで抽出してグラフ
ト率を求めると２５％であった。この得られたチタン酸
化物、高分子化合物グラフト重合体をトルエン中に分散
させると安定なコロイド分散性を示した。The reaction product was transferred into 300 wI methyl alcohol, and the resulting precipitate was collected and dried to give a polymerization yield. The polymerization rate was 50%. Furthermore, the grafting rate was determined to be 25% by extraction with benzene. When the obtained titanium oxide/high molecular compound graft polymer was dispersed in toluene, it exhibited stable colloidal dispersibility.
比較例 ｌ
実施１における酸化チタンとｎ−ブチルリチウムの反応
せずに、ただちにメチルメタクリレートを重合させると
、重合収率は４５％と重合するが、はとんどグラフトせ
ず、溶媒への分散性も良好ではなかった。Comparative Example l When methyl methacrylate is immediately polymerized without reacting titanium oxide and n-butyllithium in Example 1, the polymerization yield is 45%, but there is almost no grafting and dispersion in the solvent. Sex was also not good.
実施例 ２
実施、＠ｌにおける重合性単量体としてアクリロニトリ
ル０．５５１’を用いた。また、溶媒としてテトラヒド
ロフラン２５＠ｌを用いて、１時間の反応後、重合する
と、重合収率は４２％で、グラフト率は１４％であった
。Example 2 Acrylonitrile 0.551' was used as the polymerizable monomer in the implementation @l. Further, when polymerization was carried out after 1 hour of reaction using 25@l of tetrahydrofuran as a solvent, the polymerization yield was 42% and the grafting rate was 14%.
得られたグラフト重合体はジメチルホルムアミドに良分
散性を示した。The obtained graft polymer showed good dispersibility in dimethylformamide.
比較例 ２
実施例２において、重合性単量体に０．５２のスチレン
を用いて、１時間の触媒処理後重合したが、はとんど重
合しなかった。Comparative Example 2 In Example 2, 0.52 styrene was used as the polymerizable monomer and polymerization was carried out after 1 hour of catalyst treatment, but polymerization hardly occurred.
手続補正書
１． 事件の表示 昭和５７年特許願 ５９４５０号２
発明の名称 チタン酸化物−高分子化合物ブラット重
合体の製造方法
３、 補正をする者
事件との関係 特許出願人
住所 新潟市寺尾上六丁目１５の１９
警賢 冨芝警
■
４、補正命令の日付 昭和５７年７月９日発送日 昭和
５７年７月２７日
５、補正の対象
願書の発明者の欄および
：ｌ′１′
鮮明に記載した願書と明細書
６、補正の内容
別紙の通りProcedural amendment 1. Display of case 1982 patent application No. 59450 2
Title of the invention Method for producing titanium oxide-high molecular compound brat polymer 3 Relationship with the case of the person making the amendment Patent applicant address Tomiba Keiken 6-15-19 Teraoue, Niigata City 4. Amendment order Date: July 9, 1980 Date of dispatch: July 27, 1980 5. The inventor's column of the application subject to amendment and: l'1' The application clearly stated and specification 6, the content of the amendment as shown in the attached sheet.
Claims (1)
付加物を重合開始剤として、Ｐｒ１ｃｅ−Ａｌｆｒｅｙ
のＱ％ ｅスキームでいうｅ値が正を示し、かつＱ値が
０．１以上の重合性単量体少なくとも一種とを重合させ
ることを特徴とするチタン酸化物−高分子化合物グラフ
ト重合体の製造方法。Using an adduct obtained by reacting titanium oxide and alkyl lithium as a polymerization initiator, Pr1ce-Alfrey
A titanium oxide-polymer compound graft polymer characterized in that it has a positive e value in the e scheme and is polymerized with at least one polymerizable monomer having a Q value of 0.1 or more. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5945082A JPS58174411A (en) | 1982-04-08 | 1982-04-08 | Preparation of graft polymer of titanium oxide and polymeric compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5945082A JPS58174411A (en) | 1982-04-08 | 1982-04-08 | Preparation of graft polymer of titanium oxide and polymeric compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58174411A true JPS58174411A (en) | 1983-10-13 |
Family
ID=13113634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5945082A Pending JPS58174411A (en) | 1982-04-08 | 1982-04-08 | Preparation of graft polymer of titanium oxide and polymeric compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58174411A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0577561U (en) * | 1992-03-30 | 1993-10-22 | 国産電機株式会社 | Rotational speed controller for internal combustion engine |
| EP1393122A1 (en) | 2001-05-15 | 2004-03-03 | E Ink Corporation | Electrophoretic particles |
-
1982
- 1982-04-08 JP JP5945082A patent/JPS58174411A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0577561U (en) * | 1992-03-30 | 1993-10-22 | 国産電機株式会社 | Rotational speed controller for internal combustion engine |
| EP1393122A1 (en) | 2001-05-15 | 2004-03-03 | E Ink Corporation | Electrophoretic particles |
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