JPH09302097A - Preparation of polyimide powder - Google Patents
Preparation of polyimide powderInfo
- Publication number
- JPH09302097A JPH09302097A JP12138696A JP12138696A JPH09302097A JP H09302097 A JPH09302097 A JP H09302097A JP 12138696 A JP12138696 A JP 12138696A JP 12138696 A JP12138696 A JP 12138696A JP H09302097 A JPH09302097 A JP H09302097A
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- Japan
- Prior art keywords
- polyimide
- group
- solvent
- formula
- poor solvent
- 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.)
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- Processes Of Treating Macromolecular Substances (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリイミド溶液から
のポリイミド粉の単離法に関する。TECHNICAL FIELD The present invention relates to a method for isolating polyimide powder from a polyimide solution.
【０００２】[0002]
【従来の技術】従来からテトラカルボン酸とジアミンと
の反応により得られるポリイミドは種々の優れた物性
や、良好な耐熱性を有するためにエレクトロニクスの分
野や宇宙・航空産業分野等での利用が期待されている
が、優れた耐熱性や機械・電気特性は有しているものの
成形加工性にとぼしく、成形加工性向上の為に多くの検
討が成されている。例えば加工性向上のために溶剤溶解
性を付与したり（特開平１−２４２６６４号公報）、熱
可塑性を付与（特開平２−０１８４１９号公報等）した
ポリイミドが多く開発されてきた。2. Description of the Related Art Conventionally, polyimide obtained by the reaction of tetracarboxylic acid and diamine has various excellent physical properties and good heat resistance, and is expected to be used in the fields of electronics, aerospace industry, etc. Although it has excellent heat resistance and mechanical / electrical characteristics, it is poor in moldability and many studies have been made to improve it. For example, many polyimides have been developed which have been given solvent solubility (Japanese Patent Laid-Open No. 1-2242664) or thermoplasticity (Japanese Patent Laid-Open No. 2-018419) to improve processability.
【０００３】溶剤溶解性を有するポリイミド類として
は、下記式（４）Polyimides having solvent solubility are represented by the following formula (4)
【化５】 で表されるような基本骨格からなるポリエーテルイミド
（ゼネラル・エレクトリック社製：商品名Ｕｌｔｅｍ）
や、下記式（１）Embedded image Polyetherimide having a basic skeleton represented by (General Electric Co., Ltd .: trade name Ultem)
Or the following formula (1)
【化６】 （式中、Ｘ、Ｙ、Ｒ1及びＲ2は前記に同じ）で表される
フェノール系溶剤に可溶なポリイミドが知られている。
（特開平１−１１０５３０号公報等）[Chemical 6] A polyimide soluble in a phenolic solvent represented by the formula (X, Y, R 1 and R 2 are the same as above) is known.
(JP-A-1-110530, etc.)
【０００４】しかしながら、これら溶剤溶解性を有する
ポリイミドの多くの場合はポリイミド溶液からのポリイ
ミド粉体の単離が困難であるためにポリイミド溶液のま
までコート剤等として用いることが一般的であり、その
用途展開も限られたものとなっていた。その用途展開の
拡充を目的としてポリイミド溶液からのポリイミド粉体
の単離方法についての研究がなされている。However, in many cases of these solvent-soluble polyimides, since it is difficult to isolate the polyimide powder from the polyimide solution, it is common to use the polyimide solution as it is as a coating agent or the like. Its application development was also limited. Studies have been conducted on a method for isolating polyimide powder from a polyimide solution for the purpose of expanding its application.
【０００５】例えばポリイミド粉体単離法の検討として
は、高速撹拌させた貧溶媒中にポリイミド溶液を添加
する方法や、逆にポリイミド溶液中にポリイミドの良
溶媒と貧溶媒の混合溶媒を添加する方法（特開平３−２
４３６２９号公報）等が知られている。しかしながら、
の方法では粒状もしくはひも状のポリイミドが得られ
ることが多く、その後の残存溶媒の除去が困難なものと
なってしまう問題点があった。また、この問題点を解決
する目的で高速回転式粉砕機を併用する事により粉体化
する方法も検討されてはいるが、工業的な規模でポリイ
ミド粉を製造するためには特別な装置が必要となり現実
的な方法とはいえない。For example, as a study of the polyimide powder isolation method, a method of adding a polyimide solution to a poor solvent which is stirred at a high speed, or conversely, a mixed solvent of a good solvent of polyimide and a poor solvent is added to the polyimide solution. Method (Japanese Patent Laid-Open No. 3-2
No. 43629) is known. However,
In the method (1), a granular or string-shaped polyimide is often obtained, and there is a problem that it becomes difficult to remove the residual solvent thereafter. In addition, although a method of pulverizing by using a high-speed rotary crusher together with the object of solving this problem has been studied, a special device is required for producing polyimide powder on an industrial scale. It is necessary and not a realistic method.
【０００６】さらに加えてポリイミドはその繰り返し単
位構造の違いにより、各種溶剤に対する溶解性が異なる
ために、溶剤溶解性を有するポリイミド全てが特開平３
−２４３６２９号公報の手法で粉体単離化できない事は
容易に推測できる事である。In addition, since polyimides have different solubility in various solvents due to the difference in the repeating unit structure, all polyimides having solvent solubility are disclosed in Japanese Patent Laid-Open No. Hei 3 (1999) -311.
It can be easily inferred that powder isolation cannot be carried out by the method of Japanese Patent No. 243629.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、フェ
ノール系溶剤に溶解している式（１）で表されるポリイ
ミドを、粉体状として単離し、ポリイミド粉を得る事で
ある。SUMMARY OF THE INVENTION An object of the present invention is to obtain a polyimide powder by isolating the polyimide represented by the formula (1) dissolved in a phenolic solvent as a powder.
【０００８】[0008]
【課題を解決するための手段】本発明者等は鋭意検討し
た結果、フェノール系溶剤に溶解している式（１）で表
されるポリイミド溶液の温度を、５０℃以上貧溶媒の沸
点以下に保持し、貧溶媒と直接接触することにより容易
にポリイミド粉として単離できる事を見いだし、本発明
を完成させるに至った。Means for Solving the Problems As a result of intensive studies by the present inventors, the temperature of the polyimide solution represented by the formula (1) dissolved in a phenolic solvent is set to 50 ° C. or higher and the boiling point of the poor solvent or lower. The inventors have found that the polyimide powder can be easily isolated by holding it and directly contacting it with a poor solvent, and completed the present invention.
【０００９】すなわち、本発明は、式（１）That is, the present invention is based on the formula (1)
【化７】 （式中、Ｘは[Chemical 7] (Where X is
【化８】 から成る群より選ばれた少なくとも１つの基を表し、Ｒ
1、Ｒ2、Ｒ3は、それぞれ独立に水素原子、低級アルキ
ル基、低級アルコキシル基、フェニル基、ビフェニル
基、フェノキシ基、ビフェノキシ基、トリフルオロメチ
ル基、塩素原子、または臭素原子から成る群から選ばれ
た基を表し、Ｙは、Embedded image R represents at least one group selected from the group consisting of
1 , R 2 and R 3 are each independently a hydrogen atom, a lower alkyl group, a lower alkoxyl group, a phenyl group, a biphenyl group, a phenoxy group, a biphenoxy group, a trifluoromethyl group, a chlorine atom or a bromine atom. Represents a selected group, Y is
【化９】 から選ばれた少なくとも１つの基を示す。）で表される
繰り返し単位を有するポリイミドとフェノール系溶剤か
ら構成されるポリイミド溶液にポリイミドに対する貧溶
媒を接触させ、次いで析出する結晶を分離することを特
徴とするポリイミド粉の製造方法である。Embedded image At least one group selected from ) A polyimide solution comprising a repeating unit represented by the formula (1) and a phenolic solvent is brought into contact with a poor solvent for the polyimide, and then the precipitated crystals are separated.
【００１０】[0010]
【発明の実施の形態】本発明で使用されるポリイミド
は、ジアミン、テトラカルボン酸無水物をフェノール系
の溶媒中で触媒の存在下、又は非存在下で脱水重縮合し
て製造される。BEST MODE FOR CARRYING OUT THE INVENTION The polyimide used in the present invention is produced by dehydration polycondensation of a diamine and a tetracarboxylic acid anhydride in a phenolic solvent in the presence or absence of a catalyst.
【００１１】主に使用されるジアミンとしては、ビス
〔４−（３−アミノフェノキシ）フェニル〕メタン、
１，１−ビス〔４−（３−アミノフェノキシ）フェニ
ル〕エタン、１，２−〔４−（３−アミノフェノキシ）
フェニル〕エタン、２，２−ビス〔４−（３−アミノフ
ェノキシ）フェニル〕プロパン、２，２−ビス〔４−
（３−アミノフェノキシ）フェニル〕ブタン、２，２−
ビス〔４−（３−アミノフェノキシ）フェニル〕−１，
１，１，３，３，３，−ヘキサフルオロプロパン、４，
４−ビス（３−アミノフェノキシ）ビフェニル、ビス
〔４−（３−アミノフェノキシ）フェニル〕ケトン、ビ
ス〔４−（３−アミノフェノキシ）フェニル〕スルフィ
ド、ビス〔４−（３−アミノフェノキシ）フェニル〕ス
ルホキシド、ビス〔４−（３−アミノフェノキシ）フェ
ニル〕スルホン、ビス〔４−（３−アミノフェノキシ）
フェニル〕エーテル等が挙げられ、これらは単独あるい
は二種以上混合して用いられる。The diamines mainly used are bis [4- (3-aminophenoxy) phenyl] methane,
1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2- [4- (3-aminophenoxy)
Phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] butane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] -1,
1,1,3,3,3, -hexafluoropropane, 4,
4-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl ] Sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)
Examples thereof include phenyl] ether, and these may be used alone or in combination of two or more.
【００１２】テトラカルボン酸無水物としてはエチレン
テトラカルボン酸二無水物、シクロペンタンカルボン酸
二無水物、ピロメリット酸二無水物、３，３´，４，４
´−ベンゾフェノンテトラカルボン酸二無水物、２，２
´，３，３´−ベンゾフェノンテトラカルボン酸二無水
物、３，３´，４，４´−ビフェニルテトラカルボン酸
二無水物、２，２´，３，３´−ビフェニルテトラカル
ボン酸二無水物、２，２´−ビス（３，４−ジカルボキ
シフェニル）プロパン二無水物、２，２´−ビス（２，
３−ジカルボキシフェニル）プロパン二無水物、ビス
（３，４−ジカルボキシフェニル）エーテル二無水物、
ビス（３，４−ジカルボキシフェニル）スルホン二無水
物、１，１−ビス（２，３−ジカルボキシフェニル）エ
タン二無水物、ビス（２，３−ジカルボキシフェニル）
メタン二無水物、１，１−ビス（２，３−ジカルボキシ
フェニル）エタン二無水物、ビス（３，４−ジカルボキ
シフェニル）メタン二無水物、２，３，６，７−ナフタ
レンテトラカルボン酸二無水物、１，４，５，８−ナフ
タレンテトラカルボン酸二無水物、１，２，５，６−ナ
フタレンテトラカルボン酸二無水物、１，２，３，４−
ベンゼンテトラカルボン酸二無水物、３，４，９，１０
−ペリレンテトラカルボン酸二無水物、２，３，６，７
−アントラセンカルボン酸二無水物、１，２，７，８−
フェナントレンカルボン酸二無水物等が挙げられ、これ
らは単独あるいは二種類以上混合して用いられる。As the tetracarboxylic acid anhydride, ethylene tetracarboxylic acid dianhydride, cyclopentanecarboxylic acid dianhydride, pyromellitic dianhydride, 3,3 ', 4,4
′ -Benzophenone tetracarboxylic dianhydride, 2,2
′, 3,3′-Benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride , 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis (2,2
3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl)
Methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-
Benzenetetracarboxylic dianhydride, 3,4,9,10
-Perylenetetracarboxylic dianhydride, 2,3,6,7
-Anthracene carboxylic acid dianhydride, 1,2,7,8-
Examples thereof include phenanthrenecarboxylic acid dianhydride, which may be used alone or in admixture of two or more.
【００１３】重合に用いる溶媒としては、フェノール、
ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、ｏ
−クロロフェノール、ｐ−クロロフェノール等が挙げら
れる。これらは単独でも、あるいは二種類以上混合して
用いても差し支えない。The solvent used for the polymerization is phenol,
o-cresol, m-cresol, p-cresol, o
-Chlorophenol, p-chlorophenol, etc. are mentioned. These may be used alone or in combination of two or more.
【００１４】ポリイミドに対する貧溶媒とは、ポリイミ
ド溶液に十分な量を加えると有機溶媒を除去しなくても
ポリイミドを析出させる能力を持つ溶媒である。ここで
用いられる貧溶媒としては、メタノール、エタノール、
ｎ−プロパノール、ｉ−プロパノール、メチルエチルケ
トン、アセトン、ジエチルケトン、ｏ−ジクロロベンゼ
ン、ｐ−ジクロロベンゼン、クロロベンゼン、ベンゼ
ン、ジメチルベンゼン、トルエン等が挙げられる。The poor solvent for the polyimide is a solvent having a capability of precipitating the polyimide without removing the organic solvent when a sufficient amount of the polyimide solution is added. As the poor solvent used here, methanol, ethanol,
Examples thereof include n-propanol, i-propanol, methyl ethyl ketone, acetone, diethyl ketone, o-dichlorobenzene, p-dichlorobenzene, chlorobenzene, benzene, dimethylbenzene and toluene.
【００１５】貧溶媒とポリイミド溶液を接触させる際
は、貧溶媒をポリイミド溶液に連続的もしくは間欠的に
滴下し、その量はポリイミドの種類や溶解度、更には貧
溶媒によって異なるが、ポリイミドの理論収量に対し、
好ましくは３重量倍以上、更に好ましくは１０重量倍以
上を要する。３重量倍未満ではポリイミドが溶液中から
結晶として析出されにくく、例え析出したとしてもほと
んど濾別できない。When the poor solvent and the polyimide solution are brought into contact with each other, the poor solvent is continuously or intermittently added dropwise to the polyimide solution, and the amount thereof varies depending on the kind and solubility of the polyimide and the poor solvent. As opposed to
It is preferably 3 times by weight or more, more preferably 10 times by weight or more. If the amount is less than 3 times by weight, the polyimide is hard to be precipitated as crystals from the solution, and even if it is precipitated, it cannot be separated by filtration.
【００１６】また、貧溶媒の滴下速度は１時間当りポリ
イミドの理論収量に対して１０倍以下、更に好ましくは
６倍以下である、それ以上では貧溶媒との接触中にポリ
イミドが凝集する事がある。The dropping rate of the poor solvent is not more than 10 times, more preferably not more than 6 times the theoretical yield of polyimide per hour. Above this, the polyimide may agglomerate during contact with the poor solvent. is there.
【００１７】貧溶媒と接触させる時のポリイミド溶液の
温度は、ポリイミドの種類や貧溶媒によって異なるが、
通常５０℃以上であり上限は溶媒の沸点である。５０℃
未満で接触させると、貧溶媒との接触中にポリイミドが
凝集する。The temperature of the polyimide solution at the time of contact with the poor solvent varies depending on the type of polyimide and the poor solvent,
It is usually 50 ° C. or higher, and the upper limit is the boiling point of the solvent. 50 ℃
If contacted at less than, the polyimide will agglomerate during contact with the poor solvent.
【００１８】析出したポリイミドの結晶粉末は、加圧ろ
過や減圧ろ過などのろ過器を用いて濾別し、ポリイミド
粉を単離する。次いで、貧溶媒などのポリイミド粉を溶
解しない溶媒で数回洗浄し、重合溶媒を十分に除去す
る。その後、送風乾燥や減圧乾燥などの方法で洗浄溶媒
を除去し、ポリイミド粉を得る。The precipitated polyimide crystal powder is filtered using a filter such as pressure filtration or vacuum filtration to isolate the polyimide powder. Then, the polymerization solvent is sufficiently removed by washing several times with a solvent that does not dissolve the polyimide powder, such as a poor solvent. Then, the washing solvent is removed by a method such as blast drying or vacuum drying to obtain a polyimide powder.
【００１９】[0019]
【実施例】以下、本発明を実施例および比較例により具
体的に説明するが、本発明はこれら実施例に何等限定さ
れるものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
【００２０】実施例１ かきまぜ機、還流冷却器および窒素導入管を備えた反応
容器に、４，４’−ビス（３−アミノフェノキシ）ビフ
ェニル３６８．４４ｇ（１．０モル）、無水フタル酸２
３．７０ｇ（０．１６モル）、無水ピロメリット酸１０
４．７０ｇ（０．４８モル），ビフェニルテトラカルボ
ン酸二無水物１４１．２３ｇ（０．４８モル）およびｍ
−クレゾール１，８４０ｇを装入し、撹拌下２００℃ま
で加熱し、２００℃にて８時間保温した。この溶液の赤
外吸収スペクトルを測定した結果、ポリイミド溶液であ
る事を確認した。次いで反応溶液を８０℃に保持し、ポ
リイミド粉の理論収量の１２倍（７２２５ｇ）のトルエ
ンを２時間かけて滴下すると、滴下中にポリイミド粉が
析出してくる。この析出物を濾別し、さらにトルエンに
て洗浄を数回行なった後、窒素雰囲気下で乾燥を行な
い、５７２ｇ（収率９５．０％）のポリイミド粉を得
た。Example 1 A reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 368.44 g (1.0 mol) of 4,4'-bis (3-aminophenoxy) biphenyl and 2 phthalic anhydrides.
3.70 g (0.16 mol), pyromellitic dianhydride 10
4.70 g (0.48 mol), biphenyltetracarboxylic dianhydride 141.23 g (0.48 mol) and m
-Cresol 1,840 g was charged, heated to 200 ° C with stirring, and kept at 200 ° C for 8 hours. As a result of measuring an infrared absorption spectrum of this solution, it was confirmed to be a polyimide solution. Then, the reaction solution is kept at 80 ° C., and toluene of 12 times (7225 g) the theoretical yield of the polyimide powder is added dropwise over 2 hours, and the polyimide powder is deposited during the addition. This precipitate was separated by filtration, washed with toluene several times, and then dried under a nitrogen atmosphere to obtain 572 g (yield 95.0%) of polyimide powder.
【００２１】実施例２ 重合溶媒にｐ−クレゾールを用いた以外は実施例１と同
様に実験を行なった。トルエンを滴下中にポリイミド粉
が析出してくる。５６０ｇ（収率９３．０％）のポリイ
ミド粉を得た。Example 2 An experiment was conducted in the same manner as in Example 1 except that p-cresol was used as the polymerization solvent. Polyimide powder is deposited during the dropwise addition of toluene. 560 g (yield 93.0%) of polyimide powder was obtained.
【００２２】実施例３ 重合溶媒にフェノールを用いた以外は実施例１と同様に
実験を行なった。トルエンを滴下中にポリイミド粉が析
出してくる。５６５ｇ（収率９３．８％）のポリイミド
粉を得た。Example 3 An experiment was conducted in the same manner as in Example 1 except that phenol was used as the polymerization solvent. Polyimide powder is deposited during the dropwise addition of toluene. 565 g (yield 93.8%) of polyimide powder was obtained.
【００２３】実施例４ 反応溶液の保持温度を７０℃とし、貧溶媒としてメチル
エチルケトンをポリイミド粉の理論収量の７倍（４２１
５ｇ）を用いた以外は実施例１と同様に実験を行なっ
た。メチルエチルケトンを滴下中にポリイミドの粉体が
析出してくる。５９３ｇ（収率９８．５％）のポリイミ
ド粉を得た。Example 4 The holding temperature of the reaction solution was 70 ° C., and methyl ethyl ketone was used as a poor solvent 7 times the theoretical yield of polyimide powder (421).
An experiment was conducted in the same manner as in Example 1 except that 5 g) was used. Polyimide powder is deposited during the dropping of methyl ethyl ketone. 593 g (yield 98.5%) of polyimide powder was obtained.
【００２４】実施例５ 反応溶液の保持温度を１００℃とした以外は実施例１と
同様に実験を行なった。トルエンを滴下中にポリイミド
粉が析出してくる。５５２ｇ（収率９１．７％）のポリ
イミド粉を得た。Example 5 An experiment was conducted in the same manner as in Example 1 except that the holding temperature of the reaction solution was 100 ° C. Polyimide powder is deposited during the dropwise addition of toluene. 552 g (yield 91.7%) of polyimide powder was obtained.
【００２５】実施例６ 貧溶媒量をポリイミド粉の理論収率の４倍（２４０８
ｇ）とした以外は実施例１と同様に実験を行なった。ト
ルエンを滴下中にポリイミドの粉体が析出してくる。４
５１ｇ（収率７４．９％）のポリイミド粉を得た。収率
からみて、溶媒中にポリイミド粉は析出しきっておらず
まだ溶液中に溶け込んでいる。Example 6 The amount of poor solvent was 4 times the theoretical yield of polyimide powder (2408).
An experiment was performed in the same manner as in Example 1 except that g) was used. Polyimide powder is deposited during the dropwise addition of toluene. Four
51 g (yield 74.9%) of polyimide powder was obtained. Judging from the yield, the polyimide powder is not completely precipitated in the solvent and is still dissolved in the solution.
【００２６】実施例７ 原料のジアミンに１，３−ビス（３−アミノフェノキ
シ）ベンゼン２９２．３ｇ（１．０モル）、テトラカル
ボン酸二無水物としてビフェニルテトラカルボン酸二無
水物２８２．４５ｇ（０．９６モル）を用いた他は実施
例１と同様に実験を行なった。トルエンを滴下中にポリ
イミド粉が析出してくる。５０４ｇ（収率９３．５％）
のポリイミド粉を得た。Example 7 292.3 g (1.0 mol) of 1,3-bis (3-aminophenoxy) benzene as a starting diamine and 282.45 g of biphenyltetracarboxylic dianhydride as a tetracarboxylic dianhydride The same experiment as in Example 1 was carried out except that 0.96 mol) was used. Polyimide powder is deposited during the dropwise addition of toluene. 504g (Yield 93.5%)
Was obtained.
【００２７】実施例８ 原料のジアミンに１，３−ビス（３−アミノフェノキ
シ）ベンゼン２９２．３ｇ（１．０モル）、テトラカル
ボン酸二無水物としてベンゾフェノンテトラカルボン酸
二無水物２４８．１１ｇ（０．７７モル）及びビフェニ
ルテトラカルボン酸二無水物５５．９０ｇ（０．１９モ
ル）を用いた他は実施例１と同様に実験を行なった。ト
ルエンを滴下中にポリイミド粉が析出してくる。５５５
ｇ（収率９３．４％）のポリイミド粉を得た。Example 8 292.3 g (1.0 mol) of 1,3-bis (3-aminophenoxy) benzene as the starting diamine and 248.11 g of benzophenone tetracarboxylic dianhydride as the tetracarboxylic dianhydride (0.77 mol) and 55.90 g (0.19 mol) of biphenyltetracarboxylic dianhydride were used, and the same experiment as in Example 1 was carried out. Polyimide powder is deposited during the dropwise addition of toluene. 555
g (yield 93.4%) of polyimide powder was obtained.
【００２８】比較例１ ポリイミド溶液の保持温度を２０℃とした以外は実施例
１と同様に実験を行った。トルエンを滴下中にポリイミ
ドは凝集し、ポリイミド粉の析出、取だしは出来なかっ
た。Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that the holding temperature of the polyimide solution was 20 ° C. During the dropping of toluene, the polyimide aggregated, and the polyimide powder could not be deposited or taken out.
【００２９】[0029]
【発明の効果】本発明の方法により、加工性に優れた溶
剤可溶性のポリイミド粉を簡単に提供することができ
る。According to the method of the present invention, a solvent-soluble polyimide powder having excellent processability can be easily provided.
Claims (4)
キル基、低級アルコキシル基、フェニル基、ビフェニル
基、フェノキシ基、ビフェノキシ基、トリフルオロメチ
ル基、塩素原子、または臭素原子から成る群から選ばれ
た基を表し、 Ｙは、 【化３】 から選ばれた少なくとも１つの基を示す。）で表される
繰り返し単位を有するポリイミドとフェノール系溶剤か
ら構成されるポリイミド溶液にポリイミドに対する貧溶
媒を接触させ、次いで析出する結晶を分離することを特
徴とするポリイミド粉の製造方法。(1) Formula (1) (In the formula, X is Represents at least one group selected from the group consisting of, R 1 , R 2 , and R 3 are each independently a hydrogen atom, a lower alkyl group, a lower alkoxyl group, a phenyl group, a biphenyl group, a phenoxy group, a biphenoxy group, Represents a group selected from the group consisting of a trifluoromethyl group, a chlorine atom, or a bromine atom, and Y represents At least one group selected from ) A method for producing a polyimide powder, which comprises contacting a poor solvent for a polyimide with a polyimide solution composed of a polyimide having a repeating unit represented by the formula) and a phenolic solvent, and then separating precipitated crystals.
溶媒の沸点以下に保持して、貧溶媒と接触させることを
特徴とする請求項１記載のポリイミド粉の製造方法。2. The method for producing a polyimide powder according to claim 1, wherein the temperature of the polyimide solution is maintained at 50 ° C. or higher and not higher than the boiling point of the poor solvent and brought into contact with the poor solvent.
ことを特徴とする請求項１記載のポリイミド粉の製造方
法。3. The method for producing a polyimide powder according to claim 1, wherein the phenolic solvent is a cresol.
ール類、低級ケトン類、及び下記式（３） 【化４】 （式中、Ｋ1，Ｋ2はそれぞれ独立に水素、メチル基、ハ
ロゲン基から選ばれた基を示す。）で表される芳香族化
合物であることを特徴とする請求項１記載のポリイミド
粉の製造方法。4. A poor solvent for a polyimide is a lower alcohol, a lower ketone, and a compound represented by the following formula (3): The polyimide powder according to claim 1, which is an aromatic compound represented by the formula: wherein K 1 and K 2 each independently represent a group selected from hydrogen, a methyl group and a halogen group. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12138696A JP3591979B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing polyimide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12138696A JP3591979B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing polyimide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09302097A true JPH09302097A (en) | 1997-11-25 |
| JP3591979B2 JP3591979B2 (en) | 2004-11-24 |
Family
ID=14809922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12138696A Expired - Lifetime JP3591979B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing polyimide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3591979B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139692A (en) * | 1999-11-11 | 2001-05-22 | Hitachi Chem Co Ltd | Method for preparing polymer slurry |
| JP2004123811A (en) * | 2002-09-30 | 2004-04-22 | Jsr Corp | Polymer recovery method |
| US6916898B2 (en) | 2000-03-13 | 2005-07-12 | Mitsui Chemicals, Inc. | Process for producing polyimide |
| JP2007262333A (en) * | 2006-03-29 | 2007-10-11 | Kaneka Corp | Method for producing polyimide resin |
| JP2014070111A (en) * | 2012-09-28 | 2014-04-21 | Nippon Zeon Co Ltd | Insulator, insulating film, laminate, and method for manufacturing laminate |
| JP2016186004A (en) * | 2015-03-27 | 2016-10-27 | 三菱瓦斯化学株式会社 | Method for producing polyimide powder |
-
1996
- 1996-05-16 JP JP12138696A patent/JP3591979B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001139692A (en) * | 1999-11-11 | 2001-05-22 | Hitachi Chem Co Ltd | Method for preparing polymer slurry |
| US6916898B2 (en) | 2000-03-13 | 2005-07-12 | Mitsui Chemicals, Inc. | Process for producing polyimide |
| JP2004123811A (en) * | 2002-09-30 | 2004-04-22 | Jsr Corp | Polymer recovery method |
| JP2007262333A (en) * | 2006-03-29 | 2007-10-11 | Kaneka Corp | Method for producing polyimide resin |
| JP2014070111A (en) * | 2012-09-28 | 2014-04-21 | Nippon Zeon Co Ltd | Insulator, insulating film, laminate, and method for manufacturing laminate |
| JP2016186004A (en) * | 2015-03-27 | 2016-10-27 | 三菱瓦斯化学株式会社 | Method for producing polyimide powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3591979B2 (en) | 2004-11-24 |
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