JPH02174759A - Phthalimide compound and production thereof - Google Patents

Phthalimide compound and production thereof

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Publication number
JPH02174759A
JPH02174759A JP63328045A JP32804588A JPH02174759A JP H02174759 A JPH02174759 A JP H02174759A JP 63328045 A JP63328045 A JP 63328045A JP 32804588 A JP32804588 A JP 32804588A JP H02174759 A JPH02174759 A JP H02174759A
Authority
JP
Japan
Prior art keywords
aminobenzoate
formula
phthalimide
group
raw material
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
Application number
JP63328045A
Other languages
Japanese (ja)
Inventor
Ryuji Sato
隆二 佐藤
Toshitaka Otsuki
敏敬 大月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
Japan Synthetic Rubber Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Synthetic Rubber Co Ltd filed Critical Japan Synthetic Rubber Co Ltd
Priority to JP63328045A priority Critical patent/JPH02174759A/en
Publication of JPH02174759A publication Critical patent/JPH02174759A/en
Pending legal-status Critical Current

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  • Indole Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

NEW MATERIAL:A compound expressed by the formula (X is H or 1-4C acyl; R<1> is H, 1-10C alkyl or aryl). EXAMPLE:4-Hydroxy-N-(p-carboxyphenyl)phthalimide. USE:A raw material monomer for polyimides useful as a raw material for imide group-containing polymers having high heat resistance and also for liquid crystal polymers. PREPARATION:4-Hydroxyphthalic anhydride or an acrylated derivative thereof and 2-, 3- or 4-aminobenzoic acid or an ester derivative thereof are subjected to condensation reaction in a solvent, such as N,N-dimethylformamide, at 100-200 deg.C to afford the compound expressed by the formula.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、ポリイミドの原料上ツマ−になり得る新規な
フタルイミドに関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel phthalimide that can be used as a raw material for polyimide.

(従来の技術) ポリイミドは主鎖にイミド結合を有する最も耐熱性の優
れた樹脂の一つであり、航空機、輸送機械、コンピュー
ターなどのエレクトロニクス分野で幅広く利用されてい
る。ポリマー主鎖あるいは側鎖にイミド基を導入すると
、一般にポリマーの耐熱性が向上することが知られてお
り、イミド基含有ポリマーは耐熱性ポリマーとして研究
、利用されてきた。
(Prior Art) Polyimide is one of the most heat-resistant resins having an imide bond in its main chain, and is widely used in the electronics field such as aircraft, transportation machinery, and computers. It is known that introducing an imide group into the main chain or side chain of a polymer generally improves the heat resistance of the polymer, and imide group-containing polymers have been studied and utilized as heat-resistant polymers.

(発明が解決しようとする課題) しかしながら、これまでにイミド基含有ポリマーの原料
となる化合物としては、例えば次式:%式% (式中のR2は炭素数2〜20のアルキレン基またはア
リーレン基を示す)で示される化合物または4−ヒドロ
キシ−N −(p−ヒドロキシフェニル)フタルイミド
のようなイミド基形成性モノマーが提案されているが、
イミド基を含有するヒドロキシカルボン酸のような種々
のポリマーの原料となり得るイミド基含有モノマーは知
られていない。
(Problem to be Solved by the Invention) However, so far, as a compound serving as a raw material for an imide group-containing polymer, for example, the following formula: % formula % (R2 in the formula is an alkylene group or arylene group having 2 to 20 carbon atoms) Imide group-forming monomers such as compounds represented by
There are no known imide group-containing monomers that can be used as raw materials for various polymers such as imide group-containing hydroxycarboxylic acids.

従って本発明は、イミド基を含有するヒドロキシカルボ
ン酸を提供しようとするものである。
The present invention therefore seeks to provide hydroxycarboxylic acids containing imide groups.

(課題を解決するための手段) そこで本発明者らは、種々のイミド基含有ヒドロキシカ
ルボン酸を合成し、鋭意検討の結果、新規なフタルイミ
ドがイミド基含有ポリマーの好適な原料となることを見
出した。
(Means for Solving the Problems) Therefore, the present inventors synthesized various imide group-containing hydroxycarboxylic acids, and as a result of intensive studies, discovered that a new phthalimide can be a suitable raw material for imide group-containing polymers. Ta.

本発明の新規なフタルイミドは次式: %式% (式中のXは水素または炭素数1〜4のアシル基、R1
は水素または炭素数1〜lOのアルキル基またI はアリール基を示し、−COR’ はオルト、メタまた
はパラ位に位置している)で表される化合物である。
The novel phthalimide of the present invention has the following formula: % formula % (wherein X is hydrogen or an acyl group having 1 to 4 carbon atoms, R1
represents hydrogen or an alkyl group having 1 to 10 carbon atoms, or I represents an aryl group, and -COR' is located at the ortho, meta or para position.

この新規なフタルイミドは、4−ヒドロキシ無水フタル
酸またはそのアシル体と、2−アミノ安息香酸、3−ア
ミノ安息香酸、4−アミノ安息香酸またはそれらのエス
テル体を縮合させることによって製造することができる
This novel phthalimide can be produced by condensing 4-hydroxyphthalic anhydride or its acyl form with 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, or their ester forms. .

4−ヒドロキシ無水フタル酸のアシル体の具体例として
は4−アセトキシ無水フタル酸、4−プロピオニルオキ
シ無水フタル酸、4−ブチリルオキシ無水フタル酸が使
用できる。
Specific examples of the acyl form of 4-hydroxyphthalic anhydride include 4-acetoxyphthalic anhydride, 4-propionyloxyphthalic anhydride, and 4-butyryloxyphthalic anhydride.

アミノ安息香酸のエステルとしては、炭素数1〜12の
アルコールまたはフェノール化合物とのエステルが好ま
しく、更に好ましいのは炭素数1〜6の脂肪族アルコー
ルまたはフェノール化合物とのエステルである。そのエ
ステル体の具体例としては、2−アミノ安息香酸メチル
、3−アミノ安息香酸メチル、4−アミノ安息香酸メチ
ル、2アミノ安息香酸エチル、3−アミノ安息香酸エチ
ル、4−アミノ安息香酸エチル、2−アミノ安息香9プ
ロピル、3−アミノ安息香酸プロピル、4アミノ安息香
酸プロピル、2−アミノ安息香酸ブチル、3−アミノ安
息香酸ブチル、4−アミノ安息香酸ブチル、2−アミノ
安息香酸ペンチル、3−アミノ安息香酸ペンチル、4−
アミノ安息香酸ヘキシル、2−アミノ安息香酸ヘキシル
、3−アミノ安息香酸ヘキシル、4−アミノ安息香酸ペ
ンチル、4−アミノ安息香酸フェニル、2−7ミノ安息
香酸フエニル、3−アミノ安息香酸フェニル等が挙げら
れる。
The ester of aminobenzoic acid is preferably an ester with an alcohol having 1 to 12 carbon atoms or a phenol compound, and more preferably an ester with an aliphatic alcohol having 1 to 6 carbon atoms or a phenol compound. Specific examples of the esters include methyl 2-aminobenzoate, methyl 3-aminobenzoate, methyl 4-aminobenzoate, ethyl 2-aminobenzoate, ethyl 3-aminobenzoate, ethyl 4-aminobenzoate, 9-propyl 2-aminobenzoate, propyl 3-aminobenzoate, propyl 4-aminobenzoate, butyl 2-aminobenzoate, butyl 3-aminobenzoate, butyl 4-aminobenzoate, pentyl 2-aminobenzoate, 3- Pentyl aminobenzoate, 4-
Examples include hexyl aminobenzoate, hexyl 2-aminobenzoate, hexyl 3-aminobenzoate, pentyl 4-aminobenzoate, phenyl 4-aminobenzoate, phenyl 2-7-aminobenzoate, phenyl 3-aminobenzoate, etc. It will be done.

式(1)の母体化合物のヒドロキシカルボン酸は、実質
的に4−ヒドロキシ無水フタル酸1モルに対して、アミ
ノ安息香酸またはそのエステル1モルを反応させること
で合成できるが、この比は0.8〜1.2(モル比)で
も良好な結果を与える。
The hydroxycarboxylic acid as the parent compound of formula (1) can be synthesized by reacting 1 mole of 4-hydroxyphthalic anhydride with 1 mole of aminobenzoic acid or its ester, but this ratio is 0. Even a molar ratio of 8 to 1.2 gives good results.

反応溶媒は、0−1m−1p−クレゾール等のフェノー
ル系溶媒、N、N−ジメチルアセトアミド、N、N−ジ
メチルホルムアミド、N−メチル2−ピロリドン等のア
ミド系溶媒、氷酢酸などを用いることができる。溶媒の
量は全反応物重量の1〜2倍量以上が好ましい。反応温
度は100〜200℃が好ましい。また、縮合時に生成
する水を除去するために、ベンゼン、クロロベンゼン、
トルエン等の共沸溶媒を添加することもできるが、共沸
溶媒は存在しなくてもかまわない。
As the reaction solvent, phenolic solvents such as 0-1m-1p-cresol, amide solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl 2-pyrrolidone, and glacial acetic acid can be used. can. The amount of solvent is preferably 1 to 2 times or more the weight of all reactants. The reaction temperature is preferably 100 to 200°C. In addition, in order to remove water generated during condensation, benzene, chlorobenzene,
An azeotropic solvent such as toluene can also be added, but the azeotropic solvent does not need to be present.

反応は、通常30分〜10時間で完結する。反応混合物
を冷却後、水あるいはメタノールなどの沈澱溶媒に投入
することにより沈澱を生じさせ、濾別することにより生
成物を単離することができる。
The reaction is usually completed in 30 minutes to 10 hours. After the reaction mixture is cooled, it is poured into a precipitation solvent such as water or methanol to form a precipitate, and the product can be isolated by filtration.

更に本発明のフタルイミド化合物のうち(り式中のXが
アシル基、R1がアルキル基の化合物は前述の方法の外
に、(1)式中のXおよびRが共に水素であるフタルイ
ミド化合物をアシル化およびエステル化して合成するこ
とができる。
Furthermore, among the phthalimide compounds of the present invention (in which X is an acyl group and R1 is an alkyl group), in addition to the above-mentioned method, a phthalimide compound in which X and R in the formula (1) are both hydrogen, It can be synthesized by esterification and esterification.

このようにして得られた新規なフタルイミドは、単独で
重合に供することもできるし、他のヒドロキシカルボン
酸あるいはジヒドロキシ化合物とジカルボン酸の混合物
と重縮合することにより、ポリエステルイミド等の耐熱
性の高いポリマーを与える。また、モノマーの適切な選
択(例えば−000R1がパラ位の場合など)により液
晶性を有するポリマーも形成することができる。
The novel phthalimide thus obtained can be subjected to polymerization alone, or can be polycondensed with other hydroxycarboxylic acids or a mixture of dihydroxy compounds and dicarboxylic acids to form highly heat-resistant products such as polyesterimide. Give the polymer. Furthermore, by appropriately selecting monomers (for example, when -000R1 is at the para position), it is also possible to form a polymer having liquid crystallinity.

ここで、他のヒドロキシカルボン酸としては、p−ヒド
ロキシ安息香酸、6−ヒドロキシ−2ナフトエ酸が挙げ
られ、ジヒドロキシ化合物としては、ヒドロキノン、4
.4′−ビフェノール、ビスフェノール−A、4.4′
−ジヒドロキシジフェニルケトン、2.6−シヒドロキ
シナフタレンが挙げられ、ジカルボン酸として、テレフ
タル酸、イソフタル酸、4.4゛−ジカルボキシビフェ
ニル、2,6−ジカルボキシナフタレン等を挙げること
ができる。
Here, examples of other hydroxycarboxylic acids include p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and examples of dihydroxy compounds include hydroquinone and 4-hydroxybenzoic acid.
.. 4'-biphenol, bisphenol-A, 4.4'
Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, 4.4'-dicarboxybiphenyl, and 2,6-dicarboxynaphthalene.

(実施例) 以下、実施例に基づき本発明を具体的に説明する。(Example) Hereinafter, the present invention will be specifically explained based on Examples.

実施例1 三方コック、還流冷却管、磁気攪拌子を備えた300−
ナスフラスコに、4−ヒドロキシ無水フタル酸52.4
ミリモル、4−アミノ安息香酸52.4ミリモルおよび
N−メチル−2−ピロリドン100 mlを仕込み、窒
素雰囲気下190℃で6時間加熱攪拌した。反応混合物
を放冷汲水500−に投入し、生成物を沈澱させた。こ
れを濾別後減圧乾燥し、N。
Example 1 300- equipped with three-way cock, reflux condenser, and magnetic stirrer
In an eggplant flask, add 52.4 4-hydroxyphthalic anhydride.
52.4 mmol of 4-aminobenzoic acid and 100 ml of N-methyl-2-pyrrolidone were charged, and the mixture was heated and stirred at 190° C. for 6 hours under a nitrogen atmosphere. The reaction mixture was poured into 500 g of cooled water to precipitate the product. This was filtered and dried under reduced pressure.

N−ジメチルホルムアミドから再結晶し、41.3ミリ
モル(収率79%)の4−ヒドロキシ−N −(p−カ
ルボキシフェニル)フタルイミドを得た。このものは、
薄黄緑色の粉末で融点は361℃であった。元素分析値
は、測定値C;63.88、H;3.27、Ni5.O
O1計算値C;63.6L H;3.20、N;4.9
5であった。この化合物の赤外線吸収スペクトルおよび
プロトンNMRスペクトルを第1図および第2図に示す
Recrystallization from N-dimethylformamide gave 41.3 mmol (yield 79%) of 4-hydroxy-N-(p-carboxyphenyl)phthalimide. This thing is
It was a pale yellow-green powder with a melting point of 361°C. The elemental analysis values are measured value C: 63.88, H: 3.27, Ni5. O
O1 calculation value C; 63.6L H; 3.20, N; 4.9
It was 5. The infrared absorption spectrum and proton NMR spectrum of this compound are shown in FIGS. 1 and 2.

実施例2〜7 4−ヒドロキシ無水フタル酸の代りに表−1の八を用い
、4−アミノ安息香酸の代わりに表−1のBを用いた以
外は、実施例1と同様にして表1に示す生成物を得た。
Examples 2 to 7 Table 1 was prepared in the same manner as in Example 1, except that 8 of Table 1 was used instead of 4-hydroxyphthalic anhydride, and B of Table 1 was used instead of 4-aminobenzoic acid. The product shown in was obtained.

結果を表−1に示す。The results are shown in Table-1.

参考例1 7.65ミリモルのポリエチレンテレフタレート、12
.7ミリモルのp−ヒドロキシ安息香酸および実施例1
で得られた4−ヒドロキシ−N −(p−カルポキシフ
ヱニル)フタルイミド5.08ミリモルとを攪拌翼、窒
素ガス導入管および蒸留装置を備えたガラス容器に仕込
み、3回窒素置換した。これに2.2−の無水酢酸を加
え、窒素雰囲気下120℃で30分間加熱した。続いて
30分の間に150℃まで温度を上げ、更に1時間で2
00℃まで昇温した。
Reference example 1 7.65 mmol polyethylene terephthalate, 12
.. 7 mmol p-hydroxybenzoic acid and Example 1
5.08 mmol of 4-hydroxy-N-(p-carpoxyphenyl)phthalimide obtained above was charged into a glass container equipped with a stirring blade, a nitrogen gas introduction tube, and a distillation device, and the mixture was purged with nitrogen three times. 2.2-acetic anhydride was added to this, and the mixture was heated at 120° C. for 30 minutes under a nitrogen atmosphere. Next, the temperature was raised to 150℃ in 30 minutes, and then raised to 2℃ in 1 hour.
The temperature was raised to 00°C.

次に1.5時間で290℃まで温度を上げ、この温度で
0.5mm)Igまで減圧し、30分で反応を終了した
Next, the temperature was raised to 290° C. over 1.5 hours, and at this temperature the pressure was reduced to 0.5 mm) Ig, and the reaction was completed in 30 minutes.

加熱台材の偏光顕微鏡で、得られた重合体を観察すると
、410℃で流動を開始する液晶ポリマーであった。ま
たこのものは、フェノール/1,1゜2.2−テトラク
ロロエタン=60/40重量比の混合溶媒に不溶であっ
た。
When the obtained polymer was observed under a polarizing microscope using a heating base, it was found to be a liquid crystal polymer that started flowing at 410°C. Further, this product was insoluble in a mixed solvent having a weight ratio of phenol/1,1°2.2-tetrachloroethane=60/40.

(発明の効果) 本発明によれば新規なフタルイミドを容易に合成するこ
とができ、このフタルイミドは、分子内にイミド基およ
び反応性の水酸基とカルボン酸基を有しているので、耐
熱性の高いイミド基含有ポリマーの原料として、あるい
は液晶ポリマーの原料として好適なモノマーである。
(Effects of the Invention) According to the present invention, a novel phthalimide can be easily synthesized, and since this phthalimide has an imide group, a reactive hydroxyl group, and a carboxylic acid group in the molecule, it has excellent heat resistance. It is a monomer suitable as a raw material for polymers containing high imide groups or as a raw material for liquid crystal polymers.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は、実施例1で得られた化合物の赤外線吸収スペ
クトル図であり、 第2図は、実施例1で得られた化合物のジメチルスルホ
キシド−d4中のプロトンNMRスペクトル図である。 特許出願人日本合成ゴム株式会社
FIG. 1 is an infrared absorption spectrum diagram of the compound obtained in Example 1, and FIG. 2 is a proton NMR spectrum diagram in dimethyl sulfoxide-d4 of the compound obtained in Example 1. Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] (1)次式: ▲数式、化学式、表等があります▼( I ) (式中のXは水素または炭素数1〜4のアシル基、R^
1は水素または炭素数1〜10のアルキル基またはアリ
ール基を示す)で表されるフタルイミド化合物。
(1) The following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (X in the formula is hydrogen or an acyl group with 1 to 4 carbon atoms, R^
1 represents hydrogen or an alkyl group or aryl group having 1 to 10 carbon atoms.
(2)4−ヒドロキシ無水フタル酸またはそのアシル体
およびアミノ安息香酸またはそのエステル体を縮合させ
る請求項1記載のフタルイミド化合物の製造方法。
(2) The method for producing a phthalimide compound according to claim 1, wherein 4-hydroxyphthalic anhydride or its acyl form and aminobenzoic acid or its ester form are condensed.
JP63328045A 1988-12-27 1988-12-27 Phthalimide compound and production thereof Pending JPH02174759A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63328045A JPH02174759A (en) 1988-12-27 1988-12-27 Phthalimide compound and production thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63328045A JPH02174759A (en) 1988-12-27 1988-12-27 Phthalimide compound and production thereof

Publications (1)

Publication Number Publication Date
JPH02174759A true JPH02174759A (en) 1990-07-06

Family

ID=18205898

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63328045A Pending JPH02174759A (en) 1988-12-27 1988-12-27 Phthalimide compound and production thereof

Country Status (1)

Country Link
JP (1) JPH02174759A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017465A (en) * 1986-12-27 1991-05-21 Konica Corporation Light-sensitive silver halide photographic material
JP2011236301A (en) * 2010-05-10 2011-11-24 Okayama Univ Method for producing polyesterimide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5017465A (en) * 1986-12-27 1991-05-21 Konica Corporation Light-sensitive silver halide photographic material
JP2011236301A (en) * 2010-05-10 2011-11-24 Okayama Univ Method for producing polyesterimide

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