JPH0433809B2 - - Google Patents
Info
- Publication number
- JPH0433809B2 JPH0433809B2 JP58043982A JP4398283A JPH0433809B2 JP H0433809 B2 JPH0433809 B2 JP H0433809B2 JP 58043982 A JP58043982 A JP 58043982A JP 4398283 A JP4398283 A JP 4398283A JP H0433809 B2 JPH0433809 B2 JP H0433809B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- polymer
- aromatic
- present
- formula
- 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.)
- Expired - Lifetime
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】
本発明は新規な耐熱性熱可塑性重合体の製造法
に関するものである。更に詳しくは高温領域にお
ける良好な熱安定性及び流動性を兼備し、かつ射
出成形可能な新規可塑性芳香族ポリエーテルイミ
ド重合体の製造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 novel heat-resistant thermoplastic polymer. More specifically, the present invention relates to a method for producing a novel plastic aromatic polyetherimide polymer that has both good thermal stability and fluidity in a high temperature range and is injection moldable.
芳香族ビス（エーテル酸無水物）と芳香族ジア
ミンを重縮合させることにより、耐熱性の優れた
芳香族ポリエーテルイミドが得られることは特開
昭50−69196号等により、すでに知られている。
しかし、これまでに提案されてきた芳香族ポリエ
ーテルイミド類は、溶融成形材料として使用する
ことを目的とした場合、溶融成形時の熱安定性、
溶融成形時の流動性及び溶融成形体の物性のトー
タルバランス面で必ずしも満足されるものではな
かつた。 It is already known from JP-A-50-69196 that aromatic polyetherimide with excellent heat resistance can be obtained by polycondensing aromatic bis(ether acid anhydride) and aromatic diamine. .
However, when the aromatic polyetherimides that have been proposed so far are intended to be used as melt molding materials, the thermal stability during melt molding,
The total balance of fluidity during melt molding and physical properties of the melt molded product was not always satisfactory.
そこで、本発明者らは、300〜400℃の温度領域
において良好な熱安定性及び流動性を兼ね備える
ことにより良好な溶融成形性を有し、かつ成形体
の物性バランスのすぐれた芳香族ポリエーテルイ
ミドを得ることを目的として鋭意検討を行なつた
結果、特定の芳香族ジアミンを使用することによ
り、目的とする特性を有する新規熱可塑性芳香族
ポリエーテルイミド重合体が得られることを見出
し本発明に到達した。 Therefore, the present inventors developed an aromatic polyether that has good melt moldability by combining good thermal stability and fluidity in the temperature range of 300 to 400°C, and has an excellent balance of physical properties in molded products. As a result of extensive research aimed at obtaining imides, it was discovered that a new thermoplastic aromatic polyetherimide polymer having the desired properties could be obtained by using a specific aromatic diamine, and the present invention was created. reached.
すなわち、本発明は、
(A) 一般式（）
〔ただし、式中、Ｒは、
である〕で表わされる化合物、
(B) 必要に応じトリメリツト酸クロリド並びに
(C) 一般式（）
で表わされる化合物を重縮合反応させることを特
徴とする熱可塑性ポリエーテルイミド重合体の製
造法に関する。 That is, the present invention provides (A) general formula () [However, in the formula, R is ], (B) trimellitic acid chloride as necessary and (C) general formula () The present invention relates to a method for producing a thermoplastic polyetherimide polymer, which is characterized by subjecting a compound represented by the following formula to a polycondensation reaction.
本発明に用いられる前記一般式（）で示され
る芳香族ビス（エーテル酸無水物）の具体例とし
ては、たとえば、ビス〔４−｛３−（３，４−ジカ
ルボキシフエノキシ）フエノキシ｝フエニルスル
ホン二無水物などがある。 Specific examples of the aromatic bis(ether acid anhydride) represented by the general formula () used in the present invention include bis[4-{3-(3,4-dicarboxyphenoxy)phenoxy} Examples include phenylsulfone dianhydride.
前記一般式（）で示される芳香族ジアミンの
具体例としては例えば、
などがあげられる。 Specific examples of the aromatic diamine represented by the general formula () include: etc.
また本発明のポリエーテルイミド重合体を製造
するにあたつて、一般式（）で示される芳香族
ジアミンに、他の芳香族ジアミン類、たとえば、
メタフエニレンジアミンやジアミノジフエニルエ
ーテルなどを添加して共重合させることも可能で
あるが、これらその他の芳香族ジアミンの共重合
使用量は生成するポリエーテルイミド重合体の溶
融加工性を大幅に低下させることのない量、たと
えば全ジアミン成分の50モル％、好ましくは30モ
ル％以下に限定すべきである。 In addition, in producing the polyetherimide polymer of the present invention, other aromatic diamines, such as
It is also possible to copolymerize by adding metaphenylene diamine, diaminodiphenyl ether, etc., but the amount of copolymerization of these other aromatic diamines will greatly affect the melt processability of the resulting polyetherimide polymer. It should be limited to an amount that does not cause deterioration, such as 50 mol %, preferably 30 mol % or less of the total diamine component.
一般式（）で表わされる化合物と一般式
（）で表わされる芳香族ジアミン、さらに必要
に応じてトリメリツト酸クロリドは、有機溶媒中
で、
100〜250℃で反応させることができる。一般式
（）で表わされる化合物とトリメリツト酸クロ
リドの総量は一般式（）で表わされる化合物１
モルに対して、0.5〜２モル、好ましくは0.9〜1.1
モル使用される。反応は、脱水させつつ行なうの
が好ましく、反応終了後、反応液を冷却して、メ
タノールなどの沈殿剤中に添加して、洗浄、ロ過
して、熱可塑性ポリエーテルイミド重合体を回収
することができる。上記有機溶媒としては、Ｎ−
メチルピロリドン、ジメチルアセトアミド、ジメ
チルアセトアミド等の極性溶媒を添加するのが好
ましい。 The compound represented by the general formula (), the aromatic diamine represented by the general formula (), and optionally trimellitic acid chloride can be reacted in an organic solvent at 100 to 250°C. The total amount of the compound represented by the general formula () and trimellitic acid chloride is the compound represented by the general formula () 1
0.5 to 2 moles, preferably 0.9 to 1.1 moles
molar used. The reaction is preferably carried out while dehydrating. After the reaction is complete, the reaction solution is cooled, added to a precipitant such as methanol, washed and filtered to recover the thermoplastic polyetherimide polymer. be able to. As the organic solvent, N-
Preferably, a polar solvent such as methylpyrrolidone, dimethylacetamide, dimethylacetamide, etc. is added.
なお、一般式（）で表わされる化合物とトリ
メリツト酸クロリド（４−クロロホルミルフタル
酸無水物）は、前者10〜100モル％および後者０
〜90モル％の割合で使用されるのが好ましい。ト
リメリツト酸クロリドが多くなりすぎると本発明
の効果を達成しがたくなる。 In addition, the compound represented by the general formula () and trimellitic acid chloride (4-chloroformylphthalic anhydride) are 10 to 100 mol% of the former and 0% of the latter.
Preferably, it is used in a proportion of ~90 mol%. If the amount of trimellitic acid chloride is too large, it becomes difficult to achieve the effects of the present invention.
本発明により得られる重合体は、一般式（）
（ただし、式中、Ｒは上記一般式（）と同様で
ある）で表わされるくり返し単位を有し、トリメ
リツト酸クロリドを併用する場合は、さらに、一
般式（）
で表わされるくり返し単位を有する。 The polymer obtained by the present invention has the general formula () (However, in the formula, R is the same as the above general formula ()), and when trimellitic acid chloride is used in combination, the general formula () It has a repeating unit expressed as .
なお、本発明において得られる熱可塑性ポリエ
ーテルイミドは、上記一般式（）及び（）に
おいて、イミドカルボニル基のうち一部がアミド
カルボニル基になつているものが含まれていても
よい。 The thermoplastic polyetherimide obtained in the present invention may contain imide carbonyl groups in which a portion of the imide carbonyl groups are amide carbonyl groups in the above general formulas () and ().
本発明の芳香族ポリエーテルイミド重合体は、
圧縮成形品、放出成形品、フイルム、ワイヤ被覆
エナメル等各種の用途に利用できる。また、必要
に応じて異種重合体、添加剤、充填剤、補強剤な
どを配合することもできる。 The aromatic polyetherimide polymer of the present invention is
It can be used for various applications such as compression molded products, extrusion molded products, films, and wire-coated enamels. Further, different polymers, additives, fillers, reinforcing agents, etc. can be added as necessary.
実施例 １
72.7重量部のビス〔４−｛３−（３，４−ジカル
ボキシフエノキ）フエノキシ｝フエニル〕スルホ
ン二無水物と41重量の２，２−ビス〔４−（４−
アミノフエノキシ）フエニル〕プロパン、1000重
量部のＮ−メチルピロリドン及び300重量部のト
ルエンの混合物を室温で約１時間撹拌した後、
150℃で約１時間還流した。この際、生成する水
を共沸により留去した。更にトエン200部を加え
て、トルエンを留去しながら180℃まで昇温した
後、冷却した。反応液をメタノールに注ぎ、重合
体を単離した。得られた粉末を赤外線スペクトル
分析（172cm-1及び1770cm-1にイミドカルボニル
基の吸収あり）し、重合体が下記式のくり返し単
位からなることを確かめた。Example 1 72.7 parts by weight of bis[4-{3-(3,4-dicarboxyphenoxy)phenoxy}phenyl]sulfone dianhydride and 41 parts by weight of 2,2-bis[4-(4-
After stirring a mixture of aminophenoxy)phenyl]propane, 1000 parts by weight of N-methylpyrrolidone and 300 parts by weight of toluene at room temperature for about 1 hour,
The mixture was refluxed at 150°C for about 1 hour. At this time, the water produced was distilled off azeotropically. Further, 200 parts of toene was added, and the temperature was raised to 180° C. while distilling toluene off, and then cooled. The reaction solution was poured into methanol to isolate the polymer. The obtained powder was subjected to infrared spectral analysis (absorption of imidocarbonyl group was observed at 172 cm -1 and 1770 cm -1 ), and it was confirmed that the polymer was composed of repeating units of the following formula.
この重合体の元素分析結果は次のとおりであ
る。 The results of elemental analysis of this polymer are as follows.
実験値−Ｃ：73.02％ Ｈ：4.09％
Ｎ：2.49％ Ｓ：2.83％
Ｏ：17.57％（残部）
理論値−Ｃ：73.08％ Ｈ：4.03％
Ｎ：2.54％ Ｓ：2.91％
Ｏ：17.44％
上記重合体の高化式フローテスターでの流れ性
は6.0×10-3c.c.／Ｓ（260℃，100Kg／cm2）であつ
た。Experimental value - C: 73.02% H: 4.09% N: 2.49% S: 2.83% O: 17.57% (remainder) Theoretical value - C: 73.08% H: 4.03% N: 2.54% S: 2.91% O: 17.44% Above The flowability of the polymer using a Koka flow tester was 6.0×10 -3 cc/S (260° C., 100 Kg/cm 2 ).
また、上記重合体のジメチルホルムアミドに溶
解して、30℃で測定した還元粘度は0.52dl／ｇで
あつた。 Further, the reduced viscosity of the above polymer dissolved in dimethylformamide and measured at 30°C was 0.52 dl/g.
Claims (1)
徴とする熱可塑性ポリエーテルイミド重合体の製
造法。[Claims] 1 (A) General formula () [However, in the formula, R is ], (B) trimellitic acid chloride as necessary, and (C) general formula 1. A method for producing a thermoplastic polyetherimide polymer, which comprises subjecting a compound represented by the formula to a polycondensation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4398283A JPS59168030A (en) | 1983-03-15 | 1983-03-15 | Production of thermoplastic polyether-imide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4398283A JPS59168030A (en) | 1983-03-15 | 1983-03-15 | Production of thermoplastic polyether-imide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59168030A JPS59168030A (en) | 1984-09-21 |
| JPH0433809B2 true JPH0433809B2 (en) | 1992-06-04 |
Family
ID=12678922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4398283A Granted JPS59168030A (en) | 1983-03-15 | 1983-03-15 | Production of thermoplastic polyether-imide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59168030A (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0158732A1 (en) * | 1983-12-30 | 1985-10-23 | General Electric Company | Polyetherimide-polyethersulfoneimide copolymers |
| US4540748A (en) * | 1984-06-29 | 1985-09-10 | Union Carbide Corporation | Polyetherimides |
| US4599396A (en) * | 1984-09-04 | 1986-07-08 | General Electric Company | Crystalline polyetherimides and polyamic acid precursors therefor |
| US4883718A (en) * | 1985-02-12 | 1989-11-28 | Mitsui Toatsu Chemicals, Inc. | Flexible copper-clad circuit substrate |
| US5278276A (en) * | 1985-08-27 | 1994-01-11 | Mitsui Toatsu Chemicals, Incorporated | Polyimide and high-temperature adhesive of polyimide |
| EP0235294B1 (en) * | 1985-08-27 | 1997-11-12 | MITSUI TOATSU CHEMICALS, Inc. | Polyimides and heat-resistant adhesives comprising the same |
| JP2567375B2 (en) * | 1986-02-13 | 1996-12-25 | 三井東圧化学株式会社 | Colorless polyimide film |
| AU579511B2 (en) * | 1986-04-09 | 1988-11-24 | Mitsui Chemicals, Inc. | Polyimide resin composition |
| JPH083041B2 (en) * | 1986-06-30 | 1996-01-17 | 三井東圧化学株式会社 | Polyimide resin composition |
| JP2585552B2 (en) * | 1986-11-19 | 1997-02-26 | 三井東圧化学株式会社 | Polyimide |
| US4861855A (en) * | 1987-03-31 | 1989-08-29 | Amoco Corporation | Polyamide-imide compositions from bisphenoxyphenyl diamine tricarboxylic anhydride and tetracarboxylic dianhydride |
| DE3874223T2 (en) * | 1987-05-06 | 1993-04-08 | Mitsui Toatsu Chemicals | HEAT-RESISTABLE RESIN PREPARATION. |
| DE68919786T2 (en) * | 1988-08-15 | 1995-07-20 | Mitsui Toatsu Chemicals | Odorless salicylic acid copolymers modified by polyvalent metals, their production processes and their use as color developing agents for pressure-sensitive recording paper layers. |
| US4943682A (en) * | 1988-12-15 | 1990-07-24 | Ethyl Corporation | Production of particulate polyimide polymers |
| JP2766843B2 (en) * | 1991-04-18 | 1998-06-18 | 三井化学株式会社 | Polycarbonate resin composition |
| JP2672476B2 (en) * | 1995-03-20 | 1997-11-05 | 三井東圧化学株式会社 | Polyimide resin composition |
| JP2593635B2 (en) * | 1995-03-20 | 1997-03-26 | 三井東圧化学株式会社 | Polyimide resin composition |
| JP2672477B2 (en) * | 1995-03-20 | 1997-11-05 | 三井東圧化学株式会社 | Composition for polyimide resin |
| JP2593634B2 (en) * | 1995-03-20 | 1997-03-26 | 三井東圧化学株式会社 | New polyimide resin composition |
| JP2593636B2 (en) * | 1995-04-17 | 1997-03-26 | 三井東圧化学株式会社 | Polyimide resin composition |
| JP2764392B2 (en) * | 1996-01-24 | 1998-06-11 | 三井化学株式会社 | Method for producing polyimide for melt molding |
| JP2769497B2 (en) * | 1996-03-08 | 1998-06-25 | 三井化学株式会社 | Method for producing polyimide for melt molding |
| US7192999B2 (en) * | 2003-09-19 | 2007-03-20 | Brewer Science Inc. | Polyimides for use as high refractive index, thin film materials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5211717B2 (en) * | 1973-03-23 | 1977-04-01 | ||
| US3917643A (en) * | 1973-06-22 | 1975-11-04 | Gen Electric | Method for making polyetherimides and products produced thereby |
| JPS5176977A (en) * | 1974-12-27 | 1976-07-03 | Hitachi Ltd | HANDOTAISOSHINOHYOMENANTEI KASHORIHOHO |
| JPS5230319A (en) * | 1975-09-04 | 1977-03-08 | Nippon Hoso Kyokai <Nhk> | Compensation circuit of digital type gamma |
| US4221897A (en) * | 1979-05-09 | 1980-09-09 | General Electric Company | Method for making polyetheramide acid |
| JPS57180633A (en) * | 1981-04-30 | 1982-11-06 | Hitachi Ltd | Curable polyimide resin composition |
-
1983
- 1983-03-15 JP JP4398283A patent/JPS59168030A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59168030A (en) | 1984-09-21 |
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