JPS6017376B2 - Manufacturing method of polyamide resin - Google Patents
Manufacturing method of polyamide resinInfo
- Publication number
- JPS6017376B2 JPS6017376B2 JP7944879A JP7944879A JPS6017376B2 JP S6017376 B2 JPS6017376 B2 JP S6017376B2 JP 7944879 A JP7944879 A JP 7944879A JP 7944879 A JP7944879 A JP 7944879A JP S6017376 B2 JPS6017376 B2 JP S6017376B2
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- Prior art keywords
- polyamide resin
- tables
- formulas
- general formula
- reaction
- 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
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- Polyamides (AREA)
Description
【発明の詳細な説明】
本発明は特に耐熱性、溶解性に優れたポリアミド樹脂の
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention particularly relates to a method for producing a polyamide resin having excellent heat resistance and solubility.
詳しくは高分子主鏡中にキナゾロン環を有するポリアミ
ド樹脂の製造方法に関する。従来耐熱性ポリアミドとし
て芳香族ポリアミド、ポリアミドィミド等が知られてい
る。More specifically, the present invention relates to a method for producing a polyamide resin having a quinazolone ring in the polymer primary mirror. Aromatic polyamides, polyamideimides, and the like are conventionally known as heat-resistant polyamides.
前者は芳香環に直接結合しているカルボキシル基とアミ
/基を有する単量体を重縮合した構造を有するポリアミ
ドで、その重合方法は二酸ハラィドとジアミンを低温で
重合する脱塩酸反応を用いて行なわれている。しかし、
この反応は非常に急速に進行し、普通数分で反応が終了
するので、それにともなって副反応等を起し易いために
、その品質調整には高度の技術を必要とする。一方、後
者のポリアミドィミドは、例えばジアミン類を無水ピロ
メリット酸(またはその酸クロラィド)と反応すること
により、先ずポリアミドカルボン酸構造を有する中間体
とし、その後加熱あるいはイヒ学処理によりポリアミド
イミドに転換する方法が行なわれる。しかし、かかる方
法では、アミド酸溶液は不安定であり、溶液保存中に粘
度の低下がみられたり、ィミド環化による不溶化をとも
なうなどの欠点を有する。The former is a polyamide with a structure obtained by polycondensing a monomer having a carboxyl group directly bonded to an aromatic ring and an amine/group, and its polymerization method uses a dehydrochlorination reaction in which a diacid halide and a diamine are polymerized at low temperature. It is being done. but,
This reaction progresses very rapidly and is usually completed within a few minutes, so that side reactions are likely to occur, so advanced techniques are required for quality control. On the other hand, the latter polyamideimide is first made into an intermediate having a polyamidecarboxylic acid structure by reacting diamines with pyromellitic anhydride (or its acid chloride), and then converted into polyamideimide by heating or chemical treatment. A method of converting is performed. However, in this method, the amic acid solution is unstable, and has disadvantages such as a decrease in viscosity during solution storage and insolubilization due to imide cyclization.
また、例えばジアミン類と無水トリメリット酸とを反応
して得られるイミドカルボン酸を出発原料とする方法も
行なわれているが、この場合、前者と同様の径路をたど
るため、前者と同様の欠点を有する。本発明の特長は安
定なポリアミドを提供することにあり、かつ、耐熱性、
溶解性に優れたキナゾロン環を有するため、熱安定性に
優れたボリアミドを与えるこを特長としている。There is also a method using imidocarboxylic acid obtained by reacting diamines and trimellitic anhydride as a starting material, but in this case, it follows the same route as the former and has the same disadvantages as the former. has. The feature of the present invention is to provide a stable polyamide, which also has heat resistance,
Because it has a quinazolone ring with excellent solubility, it is characterized by providing polyamide with excellent thermal stability.
すなわち、本発明は下記一般式(1) (式中〜または または を示し(以下同じ)、 RはC弘一または を示す。That is, the present invention is based on the following general formula (1) (in the formula ~ or or (the same applies below), R is C Koichi or shows.
)であらわされる1分子中に2つのキナゾロン環を含む
ビスメチロール化合物と、一般式(ロ)
NC−R′−CN (0)(式中
R′は−(CH2)4一およびから
選ばれた2価の有機基を示す。) A bismethylol compound containing two quinazolone rings in one molecule represented by the general formula (b) NC-R'-CN (0) (wherein R' is selected from -(CH2)4- and Indicates a divalent organic group.
)で示されるジニトリル化合物とを付加反応させること
を特徴として得られるポリアミド樹脂の製造方法に関す
るものである。) The present invention relates to a method for producing a polyamide resin obtained by carrying out an addition reaction with a dinitrile compound represented by the following.
本発明の方法により得られるポリアミド樹脂はmークレ
ゾール、NNジメチルアセトアミド、NNジメチルホル
ムアミド、Nメチル2ピロリドン等の通常知られている
溶媒に可溶であり、これらの溶液から耐熱性のある強じ
んなフィルムを得ることができる。本発明において使用
される前記一般式(1)で示されるビスメチロール化合
物は、例えば次に示す方法により容易に得ることができ
る。The polyamide resin obtained by the method of the present invention is soluble in commonly known solvents such as m-cresol, NN-dimethylacetamide, NN-dimethylformamide, and N-methyl-2-pyrrolidone, and heat-resistant and tough resins can be obtained from these solutions. You can get the film. The bismethylol compound represented by the general formula (1) used in the present invention can be easily obtained, for example, by the method shown below.
即ち互いに芳香族核のオルト位に結合しているアミ/基
とカルポキシル基とを1分子中に2組有するジアミ/ジ
カルポン酸化合物例えばジアミノテレフタル酸、または
メチレンビスァントラニル酸
と、無水酢酸、あるいはペンゾィルクロラィドなどの反
応により得られる下記一般式m)で示されるピスオキサ
ジノンを出発原料とし、一般式(0)とアンモニアとの
反応により得られる下記一般式(m)のビスキナゾロ,
ンを10〜15%溶液となる量のNNジメチルホルムア
ミド、NNジメチルアセトアミドまたはNメチル2ピロ
リドンとともに加えて、130〜150℃に加熱する。That is, a diami/dicarponic acid compound having two sets of an ami/group and a carpoxyl group in one molecule that are bonded to each other at the ortho position of an aromatic nucleus, such as diaminoterephthalic acid or methylenebisanthranilic acid, and acetic anhydride; Alternatively, bisquinazolone of the following general formula (m) obtained by reacting general formula (0) with ammonia using a pisoxazinone shown by the following general formula m) obtained by reaction with penzoyl chloride etc. as a starting material,
NN dimethylformamide, NN dimethylacetamide or N methyl 2-pyrrolidone in an amount to give a 10-15% solution and heat to 130-150°C.
次に、この系に例えば一般式(m)の2.1モ/倍のホ
ルムアルデヒドを含む38%ホルマリン溶三を加え、リ
フラツクス下で1〜2時間反応さる。この間、反応が進
めば均一な溶液となる。さらに一般式(m)の1.0モ
ル倍のホルムアルデヒドを含む38%ホルマリン溶液を
加えて、3ひげリフラックスさせる。反応溶液を水中に
投入し、汝、を得、それをろ別して、一般式(1)で示
されるビスメチロール化合物を得ることができる。その
後、例えばジオキサン−NNジメチルホルムにより再結
晶を行なえばさらに純度の良いビスメチロール化合物を
得ることができる。本発明において使用されるジニトリ
ル化合物はアジポニトリル、イソフタロニトリル、およ
びテレフタロニトリルが挙げられる。本発明の方法は上
記のようにして得られる一般式(1)のビスメチロール
化合物と、上記ジニトリル化合物とを酸性溶媒中で親電
子的に行なうこ*とができる。Next, 38% formalin solution containing, for example, 2.1 moles of formaldehyde of general formula (m) is added to this system, and the reaction is carried out under reflux for 1 to 2 hours. During this time, as the reaction progresses, a homogeneous solution is formed. Further, a 38% formalin solution containing 1.0 times the molar amount of formaldehyde of general formula (m) is added, and reflux is performed. The reaction solution is poured into water to obtain a filtrate, which is then filtered to obtain a bismethylol compound represented by the general formula (1). Thereafter, by recrystallizing with, for example, dioxane-NN dimethylform, a bismethylol compound with even higher purity can be obtained. Dinitrile compounds used in the present invention include adiponitrile, isophthalonitrile, and terephthalonitrile. The method of the present invention can be carried out electrophilically by using the bismethylol compound of general formula (1) obtained as described above and the dinitrile compound described above in an acidic solvent.
すなわち、等モル量のビスメチロ−ル化合物と、ジニト
リル化合物を硫酸、酢酸、ギ酸、ポリリン酸等の酸性溶
媒、あるいはそれらの混合溶媒中で0〜50℃、2〜1
曲時間反応を行なうことで粘ちような樹脂溶液を得るこ
とができる。この溶液を水中に投入して沈澱させてポリ
アミド樹脂を分離する。この樹脂はm−クレゾール、N
Nジメチルアセトアミド等の極性溶媒に可溶であり、固
有粘度は通常0.2〜1.2塁度のものが得られる。上
記のように本発明の方法によれば、0〜50℃、2〜1
虫時間というおだやかな反応によりァミド結合を生じさ
せることができ、副反応を伴なうことなく目的とするポ
リアミド樹脂を得ることができる。That is, equimolar amounts of a bismethylol compound and a dinitrile compound are mixed in an acidic solvent such as sulfuric acid, acetic acid, formic acid, polyphosphoric acid, or a mixed solvent thereof at 0 to 50°C for 2 to 1
A viscous resin solution can be obtained by performing a time reaction. This solution is poured into water and precipitated to separate the polyamide resin. This resin is m-cresol, N
It is soluble in polar solvents such as N dimethylacetamide, and has an intrinsic viscosity of usually 0.2 to 1.2 degrees. As described above, according to the method of the present invention, 0 to 50°C, 2 to 1
An amide bond can be generated through a gentle reaction known as insect time, and the desired polyamide resin can be obtained without side reactions.
得られた樹脂はキナゾロン環を含有するため、耐熱性、
および溶解性に著しくすぐれており電気絶縁材料、例え
ば適当な溶剤に溶解して含濠ワニスとして用い、あるい
はェポキシ樹脂など他の樹脂と混合して注型に用いるな
ど種々の用途に用いることができる。その際にアルミナ
などの充填材、その他着色剤などを併用することも差し
支えない。以下実施例をあげて本発明を具体的に説明す
る。The resulting resin contains quinazolone rings, so it has good heat resistance and
It has excellent solubility and can be used for various purposes such as electrical insulating materials, such as dissolving it in an appropriate solvent and using it as a moat-containing varnish, or mixing it with other resins such as epoxy resin and using it for casting. . At that time, fillers such as alumina and other coloring agents may be used together. The present invention will be specifically explained below with reference to Examples.
なお、実施例で使用されるビスメチロール化合物の構造
式とその略号を記す。The structural formulas and abbreviations of the bismethylol compounds used in the examples are shown below.
実施例 1
濃伴器、温度計をそなえたフラスコに上記NQ−1の3
.02夕(0.01モル)と濃硫酸16夕を加え、25
『0の水浴中で均一に熔解させる。Example 1 The above NQ-1 3 was placed in a flask equipped with a concentrator and a thermometer.
.. Add 0.2 mol (0.01 mol) and concentrated sulfuric acid 16 mol, and add 25 mol.
``Melt it evenly in a water bath of 0.
液温を25qoに保つたままアジポニトリルの1.08
夕(0.01モル)を加え、8時間反応させる。反応溶
液は砧ちようであり、淡黄色を呈す。反応溶液を、こま
かく砕いた氷水500肌【中に投入し白色沈澱を得る。
該白色沈澱をろ昇りし、希炭酸ナトリウム水溶液、水、
アセトンの順で洗浄し、減圧乾燥してポリマーを得る。
このポリマーは、mークレゾール、NNジメチルアセト
アミド‘こ可溶であり、固有粘度は0.60(NNジメ
チルアセトアミド30℃で測定)であった。1.08 of adiponitrile while keeping the liquid temperature at 25qo.
Add hydroxide (0.01 mol) and react for 8 hours. The reaction solution is pale yellow in color. Pour the reaction solution into finely crushed ice water to obtain a white precipitate.
The white precipitate was filtered and mixed with dilute aqueous sodium carbonate solution, water,
Wash with acetone and dry under reduced pressure to obtain a polymer.
This polymer was soluble in m-cresol and NN dimethylacetamide, and had an intrinsic viscosity of 0.60 (measured in NN dimethylacetamide at 30°C).
このポリマーの赤外吸収スペクトルの分析では1680
弧‐1および1618伽‐1にキナゾロン環の特性吸収
が現われ、1650弧‐1および1520肌‐1にアミ
ド結合に基ずく吸収が現われ、さらに、3400の付近
のメチロール基による吸収の減少が認められ、キナゾロ
ン環含有ポリアミドの生成が確認された。実施例 2蝿
梓器、温度計をそなえたフラスコにMQ−2の3.92
夕(0.01モル)とギ酸20夕、濃硫酸2夕を加え、
25qoの水浴中で均一に溶解させる。In the analysis of the infrared absorption spectrum of this polymer, 1680
Characteristic absorption of the quinazolone ring appears at arc-1 and 1618-1, absorption based on the amide bond appears at 1650 arc-1 and 1520 skin-1, and a decrease in absorption due to the methylol group near 3400 is observed. The formation of quinazolone ring-containing polyamide was confirmed. Example 2 3.92 MQ-2 in a flask equipped with a thermometer and a thermometer
(0.01 mol), 20 mol of formic acid, and 2 mol of concentrated sulfuric acid,
Dissolve homogeneously in a 25 qo water bath.
この系にイソフタロニトリルの1.28夕(0.01モ
ル)を加え、5時間反応させる。反応溶液は粘ちようで
あり、淡黄色を呈す。実施例1と同様な処理方法でボ利
マーを得た。このポリマーの固有粘度は0.68(NN
ジメチルアセトアミド 30℃で測定)であった。実施
例1と同様にして赤外吸収スペクトルの分析により、キ
ナゾロン環含有ポリアミドの生成を確認した。実施例
3
蝿梓器、温度計をそなえたフラスコにMQ−3の5.1
6夕(0.01モル)と、テレフタロニトリルの1.2
8汐(0.01モル)とポリリン酸25夕を加え、50
℃1独特間反応させる。1.28 molar (0.01 mol) of isophthalonitrile is added to this system and reacted for 5 hours. The reaction solution is viscous and has a pale yellow color. A baller was obtained using the same treatment method as in Example 1. The intrinsic viscosity of this polymer is 0.68 (NN
dimethylacetamide (measured at 30°C). Generation of a quinazolone ring-containing polyamide was confirmed by infrared absorption spectrum analysis in the same manner as in Example 1. Example
3. 5.1 of MQ-3 in a flask equipped with a thermometer and a thermometer.
6 (0.01 mol) and 1.2 of terephthalonitrile
Add 8 Ushio (0.01 mol) and 25 mol of polyphosphoric acid, and make 50
React at 1°C for 1 hour.
反応溶液を実施例1と同様に処理して、ポリマーを得た
。このポリマーの固有粘度は0.26であった。(NN
ジメチルアセトアミド 30℃で測定)実施例1と同様
にして、赤外吸収スペクトルの分析により、キナゾロン
環含有ポリアミドの生成を確認した。実施例 4
実施例1で得られたポリマーをNNジメチルアセトアミ
ド‘こ溶解させたのちアルミ坂上に塗布し、加熱して溶
剤を除去して、黄かつ色のフィルムを得た。The reaction solution was treated in the same manner as in Example 1 to obtain a polymer. The intrinsic viscosity of this polymer was 0.26. (NN
Dimethylacetamide (measured at 30°C) In the same manner as in Example 1, the formation of a quinazolone ring-containing polyamide was confirmed by infrared absorption spectrum analysis. Example 4 The polymer obtained in Example 1 was dissolved in NN dimethylacetamide, applied to an aluminum plate, and heated to remove the solvent to obtain a yellow colored film.
このフィルムのTgは140qo付近に認められた。ま
た、熱重量分析では空気中(1ooo/分の昇温速度)
において320q0で初期の分解が起り、400qoに
おける重量減少率は10%であった。実施例 5実施例
2で得られたポリマーを用いて実施例4と同様に処理し
てフィルムを得た。The Tg of this film was found to be around 140 qo. In addition, in thermogravimetric analysis, in air (heating rate of 1ooo/min)
Initial decomposition occurred at 320qo, and the weight loss rate at 400qo was 10%. Example 5 The polymer obtained in Example 2 was treated in the same manner as in Example 4 to obtain a film.
このフィルムはあきらかなTgを示さなかった。熱重量
分析では空気中(10℃/分の昇温速度)において38
0℃で初期分解が起り10%の重量減少は44000で
起った。以上の通り本発明の方法によれば、反応温度が
低温でよく、しかも得られたポリアミド樹脂は顕著な耐
熱性を有し、工業上極めて有利なものである。This film showed no apparent Tg. Thermogravimetric analysis shows that in air (heating rate of 10°C/min) 38
Initial decomposition occurred at 0°C and a 10% weight loss occurred at 44,000°C. As described above, according to the method of the present invention, the reaction temperature may be low, and the resulting polyamide resin has remarkable heat resistance, which is extremely advantageous industrially.
Claims (1)
ビスメチロール化合物と、 一般式(II) NC−R′−CN (II) (式中R′は−(CH_2)_4−および▲数式、化
学式、表等があります▼から 選ばれた2価の有機基を示す。 )で示されるジニトリル化合物とを付加反応させること
を特徴とするポリアミド樹脂の製造方法。 2 酸性溶媒中で反応させることを特徴とする特許請求
の範囲第1項記載のポリアミド樹脂の製造方法。[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar indicates ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A bismethylol compound containing two quinazolone rings in one molecule represented by CH_3- or ▲There are mathematical formulas, chemical formulas, tables, etc.) and the general formula (II) NC-R'-CN (II) ( In the formula, R' represents a divalent organic group selected from -(CH_2)_4- and ▲There are mathematical formulas, chemical formulas, tables, etc.). Method for producing polyamide resin. 2. The method for producing a polyamide resin according to claim 1, wherein the reaction is carried out in an acidic solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7944879A JPS6017376B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7944879A JPS6017376B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS562323A JPS562323A (en) | 1981-01-12 |
JPS6017376B2 true JPS6017376B2 (en) | 1985-05-02 |
Family
ID=13690155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7944879A Expired JPS6017376B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6017376B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62172085U (en) * | 1986-04-22 | 1987-10-31 | ||
JPS63172678U (en) * | 1987-04-28 | 1988-11-09 | ||
JPS63172677U (en) * | 1987-04-28 | 1988-11-09 |
-
1979
- 1979-06-20 JP JP7944879A patent/JPS6017376B2/en not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62172085U (en) * | 1986-04-22 | 1987-10-31 | ||
JPS63172678U (en) * | 1987-04-28 | 1988-11-09 | ||
JPS63172677U (en) * | 1987-04-28 | 1988-11-09 |
Also Published As
Publication number | Publication date |
---|---|
JPS562323A (en) | 1981-01-12 |
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