JPS6017375B2 - Manufacturing method of polyamide resin - Google Patents
Manufacturing method of polyamide resinInfo
- Publication number
- JPS6017375B2 JPS6017375B2 JP7944779A JP7944779A JPS6017375B2 JP S6017375 B2 JPS6017375 B2 JP S6017375B2 JP 7944779 A JP7944779 A JP 7944779A JP 7944779 A JP7944779 A JP 7944779A JP S6017375 B2 JPS6017375 B2 JP S6017375B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- reaction
- general formula
- tables
- 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
Links
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- Polyamides (AREA)
Description
【発明の詳細な説明】
本発明は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 relates to a method for producing a polyamide resin having excellent heat resistance and solubility.
詳しくは高分子毅にキナゾロン環を有するボリアミド樹
脂の製造方法に関する。従釆耐熱性ボリアミドとして、
芳香族ポリァミドやポリアミドィミド等が知られている
。Specifically, the present invention relates to a method for producing a polyamide resin having a quinazolone ring in the polymer. As a secondary heat-resistant polyamide,
Aromatic polyamides, polyamideimides, and the like are known.
前者のものは芳香族環に直接結合したカルボキシル基と
アミノ基を有する単量体を軍縮合した構造のポリアミド
であり、その重合方法はカルボキシル基とアミ／基を直
接高温で反応させる方法。あるいは二酸ハライドとジア
ミンを低温で反応させる方法等がある。直接反応させる
には通常２００℃以上の過酷な反応条件等を必要とする
し、また、脱塩酸反応を用いて行なう場合、その反応は
非常に急速に進行し、普通数分で終了するため、それに
伴なう副反応等が引き起されやすく、品質調整には高度
の技術を必要とする。一方、後者のボリアミドイミドに
おいても、ィミド孫含有モノマーを用いる場合、前者と
同様の径路をたどる場合が多く、やはり前者同機の欠点
を有する。本発明の目的は安定なポリアミド樹脂を提供
することにあり、かつ耐熱性、溶解性に優れたキナゾロ
ン環を有することにより、熱安定性の優れたボリアミド
が得られるという特長を有している。The former is a polyamide with a structure in which a monomer having a carboxyl group directly bonded to an aromatic ring and an amino group are condensed, and the polymerization method is to directly react the carboxyl group and the amino group at high temperature. Alternatively, there is a method in which a diacid halide and a diamine are reacted at a low temperature. Direct reaction usually requires harsh reaction conditions of 200°C or higher, and when dehydrochlorination is used, the reaction proceeds very rapidly and usually ends in a few minutes. Side reactions are likely to occur, and quality control requires advanced technology. On the other hand, in the case of the latter polyamide-imide, when an imide grandchild-containing monomer is used, the same route as the former is often followed, and it still has the same drawbacks as the former. An object of the present invention is to provide a stable polyamide resin, which has a quinazolone ring with excellent heat resistance and solubility, and has the feature that a polyamide with excellent thermal stability can be obtained.
すなわち、本発明は下記一般式０１（式中Ｒ，は−Ｃ比
−、
および
から選ばれた２価の有機基
を示す。That is, the present invention represents a divalent organic group selected from the following general formula 01 (wherein R is -C ratio-).
）で示される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（０）
ＮＣ−Ｒ２−ＣＮ （０）（式中Ｒ２
は一（ＣＱ）４−およびから
選ばれた２価の有機基を示す。) and a bismethylol compound containing two quinazolone rings in one molecule represented by the general formula (0) NC-R2-CN (0) (wherein R2
represents a divalent organic group selected from mono(CQ)4- and
）で示されるジニトリル化合物とを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に関するものである
。) The present invention relates to a method for producing a polyamide resin, which is characterized by reacting a dinitrile compound represented by the following formula.
本発明によって得られるポリアミド樹脂は、ｍ−クレゾ
ール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。生成するボリアミド
樹脂の構造は
となる。The polyamide resin obtained by the present invention is soluble in commonly known solvents such as m-cresol N.N dimethylacetamide, N.N dimethylformamide, and N-methyl 2-pyrrolidone, and can be obtained from these solutions with heat-resistant A strong film can be obtained. The structure of the polyamide resin produced is as follows.
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、以下に述べる方法に
より容易に得ることができる。The bismethylol compound represented by the general formula (1) used in the present invention can be easily obtained, for example, by the method described below.
即ちアントラニル酸と、マロン酸クロライド、あるいは
、テレフタル酸クロラィド等と反応させたのち、無水只
酢酸などで脱水閉窮させて得られる下記一般式（式中Ｒ
，は前記した２価の有機基を示す。That is, the following general formula (in the formula R
, represents the above-mentioned divalent organic group.
）で示されるビスオキサジノン化合物を出発嬢料とし、
この一般式（ｍ）の化合物とアンモニアとの反応により
得られる下記一般式（Ｗ）のピスーキナゾロン化合物を
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。
リドンと、ともに加え、１３０〜１５ぴ０に加熱する。
（式中Ｒ，は前記した２価の有機基を示す。) as a starting material,
NN dimethylformamide, NN dimethylacetamide, or N-methyl 2P in an amount to give a 10 to 15% solution of the pisuquinazolone compound of the following general formula (W) obtained by the reaction of the compound of the general formula (m) with ammonia.
Add the lidone and heat to 130-150 mph.
(In the formula, R represents the above-mentioned divalent organic group.
）ついでこの系に例えば一般式（Ｗ）の２．１モル倍の
ホルムアルデヒドを含んだ総％ホルマリン溶液を加え、
１〜２時間リフラックスさせる。反応系はこの間に均一
な溶液となる。さらに、一般式（Ｗ）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、
３０分間リフラツクスさせる。反応溶液を水中に投入し
て沈磯を得、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。) Then, to this system, for example, a total percent formalin solution containing 2.1 times the molar amount of formaldehyde of the general formula (W) is added,
Reflux for 1-2 hours. During this time, the reaction system becomes a homogeneous solution. Furthermore, a 38% formalin solution containing 1.0 times the mole of formaldehyde of general formula (W) was added,
Reflux for 30 minutes. The reaction solution is poured into water to obtain a precipitate, which is filtered to obtain a bismethylol compound represented by the general formula (1).
その後、例えばジオキサンーＮＮジメチルホルムアミド
により再結晶することにより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。また、本発明におい
て使用される上記一般式（ｍで表わされるジニトリル化
合物として、例えば、アジボニトリル、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。Thereafter, a bismethylol compound with even higher purity can be obtained by recrystallizing with dioxane-NN dimethylformamide, for example. Furthermore, examples of the dinitrile compound represented by the general formula (m) used in the present invention include adibonitrile, isophthalonitrile, and terephthalonitrile.
尚、これらジニトリル化合物は２種類以上の混合物とし
て＊使用してもなんらさしつかえることはない。本発明
の方法は上記で示される一般式（１）のピスメチロール
化合物と一般式（０）のジニトリル化合物とを酸性溶媒
中で親蟹子的に行なうことができる。すなわち、望まし
くは等モル量のビスメチロール化合物とジニトリル化合
物を、例えば硫酸、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母
時間反応を行なことで樹脂溶液を得ることができ、この
溶液を水中に投入してポリアミド樹脂を沈澱として分離
取得することができる。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０．２〜１．０の値を示す。上記の如く、本発明
によれば０〜５０００、２〜１５時間というおだやかな
条件下で反応を進行させることによりアミド結合を生じ
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。Note that there is no problem in using these dinitrile compounds as a mixture of two or more types. The method of the present invention can be carried out by using the above-mentioned pismethylol compound of general formula (1) and the dinitrile compound of general formula (0) in an acidic solvent. That is, desirably equimolar amounts of a bismethylol compound and a dinitrile compound are reacted 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 hour. By doing this, a resin solution can be obtained, and this solution can be poured into water to separate and obtain the polyamide resin as a precipitate. This resin is m-cresol, N
It is soluble in polar solvents such as N dimethylacetamide and exhibits an intrinsic viscosity of 0.2 to 1.0. As described above, according to the present invention, amide bonds can be produced by proceeding the reaction under mild conditions of 0 to 5,000 hours and 2 to 15 hours, and the desired polyamide can be produced without side reactions. Resin can be obtained.
か）るポリアミド樹脂はキナゾロン環を含有しているた
め、耐熱性、溶解性に優れた性質を持つており、電気絶
縁材料、例えば適当な溶媒に溶解して含浸ワニスとして
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。なお
その際にアルミナなどの充填材、あるいは着色剤などを
併用することも差し支えない。以下実施例をあげて、本
発明の具体的な説明を行なう。実施例で使用するビスメ
チロール化合物の構造式とその略号は下記のとおりであ
る。Since the polyamide resin contains a quinazolone ring, it has excellent heat resistance and solubility, and can be used as an electrical insulating material, for example, as an impregnating varnish by dissolving it in an appropriate solvent, or as an epoxy resin. It can be used for various purposes such as mixing with other resins and using it for casting. Note that at this time, fillers such as alumina or colorants may also be used together. The present invention will be specifically explained below with reference to Examples. The structural formulas and abbreviations of the bismethylol compounds used in the examples are as follows.
ＭＱ‐１；
ＭＱ−２；
ＭＱ−３；
実施例 １
損梓器、温度計をそなえたフラスコにＭＱ−１の３．６
＆（０．０１モル）と濃硫酸１繋を加えて、均一に溶解
させたのち２５℃に保つ。MQ-1; MQ-2; MQ-3; Example 1 3.6 of MQ-1 was placed in a flask equipped with a strainer and a thermometer.
& (0.01 mol) and one portion of concentrated sulfuric acid, and after uniformly dissolving it, keep it at 25°C.
反応温度を２５℃に保つたまま、アジポニトリルの１．
０斑（０．０１モル）を加え８時間縄洋を続ける。反応
後、樹脂液をこまかく砕いた氷水中に投入し、白色沈澱
を生じさす。この沈澱をろ別して、希炭酸ナトリワム水
溶液、水、アセトンの順に洗浄し、減圧乾燥してポリマ
ーを得る。このポリマーは、ｍクレゾール、ＮＮジメチ
ルアセトアミド、Ｎメチル２ビロリドンに可溶であり、
固有粘度は０．班（ＮＮジメチルアセトアミド中３び○
で測定）であった。1. of adiponitrile while maintaining the reaction temperature at 25°C.
Add 0 spots (0.01 mol) and continue to use the rope for 8 hours. After the reaction, the resin solution is poured into finely crushed ice water to form a white precipitate. The precipitate is filtered, washed successively with dilute aqueous sodium carbonate solution, water, and acetone, and dried under reduced pressure to obtain a polymer. This polymer is soluble in m-cresol, NN-dimethylacetamide, N-methyl-2-virolidone,
Intrinsic viscosity is 0. Group (NN dimethylacetamide 3bi○
).
また、赤外吸収スペクトルによる分析では、１６７＆ス
‐１、および１６１０の‐１にキナゾロン壕の特有な吸
収があり、１６５０仇‐１および１５２反か‐１にアミ
ド結合に基ずく吸収が現われた。さらに、３４０瓜ネ‐
１付近のメチロール基による吸収の消失が認められ、キ
ナゾロン環含有ポリアミドの生成が認められた。実施例
２
縄杵器、温度計をそなえたフラスコにＭＱ一２の４．２
６ｇ（０．０１モル）とギ酸２咳と濃硫酸滋を加え、均
に溶解させる。In addition, infrared absorption spectrometry analysis revealed that 167&su-1 and 1610-1 had absorption characteristic of quinazolone moieties, and 1650-1 and 152-1 had absorption based on amide bonds. . In addition, 340 cucumbers
Absorption due to the methylol group near 1 was observed to disappear, and formation of a quinazolone ring-containing polyamide was observed. Example 2 4.2 of MQ-2 in a flask equipped with a rope pestle and a thermometer.
Add 6 g (0.01 mol), 2 drops of formic acid and 2 drops of concentrated sulfuric acid, and dissolve evenly.
反応温度を２５℃に保つたまま、イソフタロニトリルの
１．２滋（０．０１モル）を加え、１加持間反応を続け
る。反応後、実施例１と同様に処理して、ポリマーを得
る。固有粘度は０．６５（ＮＮジメチルァセトアミド中
３０℃で測定）であった。実施例１と同様に、赤外吸収
スペクトル分析により、キナゾロン環含有ポリアミド樹
脂であることが確認された。While maintaining the reaction temperature at 25° C., 1.2 g (0.01 mol) of isophthalonitrile is added and the reaction is continued for one holding period. After the reaction, the same treatment as in Example 1 is carried out to obtain a polymer. The intrinsic viscosity was 0.65 (measured in NN dimethylacetamide at 30°C). As in Example 1, it was confirmed by infrared absorption spectrum analysis that it was a quinazolone ring-containing polyamide resin.
実施例 ３
縄梓器、温度計をそなえたフラスコに、ＭＱ−３の５．
１雛（０．０１モル）とポリリン酸２舷を加え、５ぴ○
のオイル格にフラスコを保持する。Example 3 5. of MQ-3 was added to a flask equipped with a rope strainer and a thermometer.
Add 1 chick (0.01 mol) and 2 sides of polyphosphoric acid, and make 5 pi○
Keep the flask in the oil container.
反応温度を５０℃に保ち、テレフタロニトリルの１．２
滋（０．０１モル）を加え、ｌｑ時間反応を続ける。反
応後、実施例１と同様に処理して、ポリマーを得る。固
有粘度は０．２４（ＮＮジメチルアセトアミド中３ぴ○
で測定）の値を示した。実施例１と同様、赤外吸収スペ
クトル分析により、キナゾロン環含有ポリアミド樹脂で
あることが確認された。The reaction temperature was maintained at 50°C, and 1.2% of terephthalonitrile was
Add soybean paste (0.01 mol) and continue the reaction for 1q hours. After the reaction, the same treatment as in Example 1 is carried out to obtain a polymer. Intrinsic viscosity is 0.24 (NN 3 pi in dimethylacetamide)
(measured at ). As in Example 1, it was confirmed by infrared absorption spectrum analysis that it was a quinazolone ring-containing polyamide resin.
試験例 １〜３実施例１〜３で得られた樹脂を、ＮＮジ
メチルアセトアミドに溶解させたのち、それぞれをアル
ミ坂上に塗布したのち、乾燥させることによりフィルム
を得た。Test Examples 1 to 3 After dissolving the resins obtained in Examples 1 to 3 in NN dimethylacetamide, each was applied onto an aluminum slope and dried to obtain a film.
実施例１〜２から生成したポリマーは強じんであったが
、実施例３で得られたものは強じんさはなかった。空気
中の熱重量分析を昇溢速度１ぴ○／分で測定した。その
結果を表１に示す。表１The polymers produced from Examples 1-2 were tough, while those obtained in Example 3 were not. Thermogravimetric analysis in air was carried out at an overflow rate of 1 pi/min. The results are shown in Table 1. Table 1
Claims (1)
メチロール化合物と、 一般式（II） ＮＣ−Ｒ＿２−ＣＮ （II） （式中Ｒ＿２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反応せしめることを
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 (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is -CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.) and ▲There are mathematical formulas, chemical formulas, tables, etc. A bismethylol compound containing two quinazolone rings in one molecule represented by ▼ represents a divalent organic group selected from is -(CH_2)_4-, and ▲ formula,
There are chemical formulas, tables, etc. Showing the divalent organic group selected from ▼. ) A method for producing a polyamide resin, which comprises reacting with a dinitrile compound represented by: 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 |
|---|---|---|---|
| JP7944779A JPS6017375B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7944779A JPS6017375B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS562322A JPS562322A (en) | 1981-01-12 |
| JPS6017375B2 true JPS6017375B2 (en) | 1985-05-02 |
Family
ID=13690128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7944779A Expired JPS6017375B2 (en) | 1979-06-20 | 1979-06-20 | Manufacturing method of polyamide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6017375B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07149090A (en) * | 1993-05-24 | 1995-06-13 | Morningstar Inc | Notebook binder |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SI2223922T1 (en) * | 2000-04-25 | 2016-04-29 | Icos Corporation | Inhibitors of human phosphatidyl-inositol 3-kinase delta |
| US6667300B2 (en) | 2000-04-25 | 2003-12-23 | Icos Corporation | Inhibitors of human phosphatidylinositol 3-kinase delta |
| LT2612862T (en) | 2004-05-13 | 2017-01-25 | Icos Corporation | Quinazolinones as inhibitors of human phosphatidylinositol 3-kinase delta |
| US9492449B2 (en) | 2008-11-13 | 2016-11-15 | Gilead Calistoga Llc | Therapies for hematologic malignancies |
| EP2411391A1 (en) | 2009-03-24 | 2012-02-01 | Gilead Calistoga LLC | Atropisomers of2-purinyl-3-tolyl-quinazolinone derivatives and methods of use |
| CA2759724A1 (en) | 2009-04-20 | 2010-10-28 | Calistoga Pharmaceuticals, Inc. | Methods of treatment for solid tumors |
| US8691829B2 (en) | 2009-07-21 | 2014-04-08 | Gilead Calistoga Llc | Treatment of liver disorders with PI3K inhibitors |
| AP2014007875A0 (en) | 2012-03-05 | 2014-08-31 | Gilead Calistoga Llc | Polymorphic forms of (S)-2-(1-(9H-purin-6-ylamino)propyl)-5-fluoro-3-phenylquinazolin-4(3H)-one |
| US9708327B2 (en) | 2013-12-20 | 2017-07-18 | Gilead Calistoga Llc | Polymorphic forms of a hydrochloride salt of (S)-2-(1-(9H-purin-6-ylamino)propyl)-5-fluoro-3-phenylquinazolin-4(3H)-one |
| US9567337B2 (en) | 2013-12-20 | 2017-02-14 | Gilead Calistoga Llc | Process methods for phosphatidylinositol 3-kinase inhibitors |
| MX2016016530A (en) | 2014-06-13 | 2017-03-27 | Gilead Sciences Inc | Phosphatidylinositol 3-kinase inhibitors. |
-
1979
- 1979-06-20 JP JP7944779A patent/JPS6017375B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07149090A (en) * | 1993-05-24 | 1995-06-13 | Morningstar Inc | Notebook binder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS562322A (en) | 1981-01-12 |
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