JPH01123832A - Production of aromatic polyamide-imide resin - Google Patents
Production of aromatic polyamide-imide resinInfo
- Publication number
- JPH01123832A JPH01123832A JP28197987A JP28197987A JPH01123832A JP H01123832 A JPH01123832 A JP H01123832A JP 28197987 A JP28197987 A JP 28197987A JP 28197987 A JP28197987 A JP 28197987A JP H01123832 A JPH01123832 A JP H01123832A
- Authority
- JP
- Japan
- Prior art keywords
- amic acid
- aromatic
- aromatic polyamide
- formula
- polyamide
- 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.)
- Granted
Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 33
- 229920005989 resin Polymers 0.000 title claims abstract description 11
- 239000011347 resin Substances 0.000 title claims abstract description 11
- 239000004962 Polyamide-imide Substances 0.000 title claims description 12
- 229920002312 polyamide-imide Polymers 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 26
- -1 phenylene, methylenediphenylene Chemical group 0.000 claims abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AJPUIVHOKJQSFX-UHFFFAOYSA-N 1-n,4-n-bis(trimethylsilyl)benzene-1,4-diamine Chemical compound C[Si](C)(C)NC1=CC=C(N[Si](C)(C)C)C=C1 AJPUIVHOKJQSFX-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は高重合度の芳香族ポリアミド−イミド樹脂の新
規な製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel method for producing aromatic polyamide-imide resins with a high degree of polymerization.
（従来の技術）
芳香族ポリアミド−イミド樹脂は、すでに耐熱性樹脂と
して実用化されているものでり、芳香族ポリアミド−ア
ミド酸を加熱処理もしくは化学的処理することにより製
造されることが知られている。さらに芳香族ポリアミド
−アミド酸は、芳香族ジアミンと芳香族無水トリカルボ
ン酸クロリドとを非プロトン性有機溶媒中で反応せしめ
ることによって製造されることが知られている。(Prior art) Aromatic polyamide-imide resin has already been put into practical use as a heat-resistant resin, and it is known that it can be produced by heating or chemically treating aromatic polyamide-amic acid. ing. Furthermore, it is known that aromatic polyamide-amic acid can be produced by reacting an aromatic diamine and an aromatic tricarboxylic anhydride chloride in an aprotic organic solvent.
（発明が解決しようとする問題点）
芳香族ポリアミド−イミド樹脂の重合度は、前駆体であ
る芳香族ポリアミド−アミド酸の重合度が直接反映され
るが、しかし、高重合度を意味する高い固有粘度をもつ
芳香族ポリアミド−アミド酸の製造が困難であり、また
、製造の際に使用し得る非プロトン性有機溶媒の種類も
限定されるという問題点を有していた。(Problem to be Solved by the Invention) The degree of polymerization of aromatic polyamide-imide resin is a direct reflection of the degree of polymerization of aromatic polyamide-amic acid, which is a precursor. It is difficult to produce an aromatic polyamide-amic acid having an inherent viscosity, and the types of aprotic organic solvents that can be used during production are also limited.
（問題点を解決するための手段）
本発明者は、高重合度の芳香族ポリアミド−アミド酸を
広範囲の有機溶媒を用いて製造する方法について検討を
行ない、芳香族ジアミンの代りにＮ−シリル化芳香族ジ
アミンを用いることによりこの目的を達成し得ることを
見出し、本発明に到達した。(Means for Solving the Problems) The present inventors investigated a method for producing aromatic polyamide-amic acid with a high degree of polymerization using a wide range of organic solvents, and found that N-silyl instead of aromatic diamine was used. The inventors have discovered that this object can be achieved by using aromatic diamines, and have arrived at the present invention.
すなわち、本発明は、−数式
％式％：１
（式中、Ａｒはフェニレン、メチレンジフェニレン、オ
キシジフェニレンよりなる群から選ばれた二価の芳香族
基を示す）で表されるＮ−シリル化芳香族ジアミンと無
水トリメリド酸クロリドとを非プロトン性有機溶媒中で
反応させて、−数式（式中、Ａｒはフェニレン、メチレ
ンジフェニレン、オキシジフェニレンよりなる群から選
ばれた二価の芳香族基を示し、ｎは１０〜１００の整数
を示す）で表される芳香族ポリアミド−アミド酸誘導体
を製造し、引き続いてイミド化処理することを特徴とす
る、−数式
（式中、Ａｒハフェニレン、メチレンジフェニレン、オ
キシジフェニレンよりなる群から選ばれた二価の芳香族
基を示し、ｎは１０〜１００の整数を示す）で表される
芳香族ポリアミド−イミド樹脂の製造方法である。That is, the present invention provides N- represented by the formula % formula %: 1 (wherein Ar represents a divalent aromatic group selected from the group consisting of phenylene, methylene diphenylene, and oxydiphenylene). A silylated aromatic diamine and trimellidic anhydride chloride are reacted in an aprotic organic solvent to form a divalent compound selected from the group consisting of - formula (wherein Ar is phenylene, methylene diphenylene, and oxydiphenylene). an aromatic group, n is an integer of 10 to 100), and is characterized in that it is subsequently subjected to imidization treatment, A method for producing an aromatic polyamide-imide resin represented by a divalent aromatic group selected from the group consisting of haphenylene, methylene diphenylene, and oxydiphenylene, where n is an integer of 10 to 100. .
（発明の構成）
本発明をさらに詳細に説明する。前記−数式（１）で示
されるＮ−シリル化芳香族ジアミンは相当する芳香族ジ
アミンをトリエチルアミン等の第三級アミンの存在下に
トリメチルクロロシランと反応させることにより得られ
る〔例えば、Ｊ、Ｐ。(Structure of the Invention) The present invention will be explained in further detail. The N-silylated aromatic diamine represented by formula (1) can be obtained by reacting the corresponding aromatic diamine with trimethylchlorosilane in the presence of a tertiary amine such as triethylamine [for example, J, P.
Ｋｌｅｂｅ、 Ｊ、Ｐｏｌｙｗ、 Ｓｅｔ、、 Ｐａｒ
ｔ Ｂ、 Ｖｏｌ−２＋ ｐ、１０７９（１９６４）
） 、かかるＮ−シリル化芳香族ジアミンを構成する芳
香族ジアミンの代表的な例としては、メタフェニレンジ
アミン、バラフェニレンジアミン、３．３′−ジアミノ
ジフェニルメタン、４゜４′−ジアミノジフェニルメタ
ン、３．４１−ジアミノジフェニルメタン、３．３’−
ジアミノジフェニルエーテル、４．４’−ジアミノジフ
ェニルエーテル、３．４’−ジアミノジフェニルエーテ
ル等をあげることができる。Klebe, J., Polyw, Set,, Par.
tB, Vol-2+ p, 1079 (1964)
), typical examples of aromatic diamines constituting such N-silylated aromatic diamines include metaphenylene diamine, paraphenylene diamine, 3.3'-diaminodiphenylmethane, 4°4'-diaminodiphenylmethane, 3. 41-diaminodiphenylmethane, 3.3'-
Examples include diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenyl ether.
上記−数式（ＩＩ）で表される芳香族ポリアミド−アミ
ド酸誘導体は非プロトン性有機溶媒中でＮ−シ、リル化
芳香族ジアミンと無水トリメリド酸クロリドとを通常等
モル反応させることによって製造される。使用される非
プロトン性有機溶媒の具体的な例としては、ジメチルア
セトアミド、Ｎ−メチル−２−ピロリドン、テトラメチ
ル尿素、ヘキサメチルホスホルアミドなどのアミド系溶
媒、ベンゼン、トルエン、アニソール、ニトロベンゼン
、ベンゾニトリル、等の芳香族系溶媒、ジブチルエーテ
ル、テトラヒドロフラン、ジオキサン、ジ（メトキシエ
チル）エーテル等のエーテル系溶媒、クロロホルムをは
じめとするハロゲン化炭化水素系溶媒等があげられる。The aromatic polyamide-amic acid derivative represented by formula (II) above is usually produced by reacting an N-cy, lylated aromatic diamine and trimellidic anhydride in an equimolar amount in an aprotic organic solvent. Ru. Specific examples of aprotic organic solvents used include dimethylacetamide, N-methyl-2-pyrrolidone, tetramethylurea, amide solvents such as hexamethylphosphoramide, benzene, toluene, anisole, nitrobenzene, Examples include aromatic solvents such as benzonitrile, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, di(methoxyethyl) ether, and halogenated hydrocarbon solvents such as chloroform.
これらの有機溶媒の中で、高重合度の芳香族ポリアミド
−アミド酸誘導体を得る目的のためには、ジメチルアセ
トアミドやＮ−メチル−２−ピロリドンを用いると好結
果が得″られる。Among these organic solvents, good results can be obtained by using dimethylacetamide and N-methyl-2-pyrrolidone for the purpose of obtaining aromatic polyamide-amic acid derivatives with a high degree of polymerization.
（作 用）
このような有機溶媒中でＮ−シリル化芳香族ジアミンと
無水トリメリド酸クロリドとを反応させ、上記−数式（
ｎ）で表される芳香族ポリアミド−アミド酸誘導体を製
造する具体的な方法は、通常の低温溶液重合法と特に変
わらない。すなわち、まずＮ−シリル化芳香族ジアミン
を非プロトン性有機溶媒に溶解した後、通常−５０〜＋
８０″Ｃ程度、好ましくは一２０〜＋５０°Ｃで溶液を
撹はんしながら、無水トリメリド酸クロリドを粉末状で
、または有機溶媒に溶解した溶液状で、−度にまたは徐
々に添加して反応を行なわせる。反応は直ちに起こり反
応物の粘度が上昇して行く。通常３時間から２４４時間
撹んを続けるが、場合によっては１時間以内に反応が完
結することもある。反応が終了した反応物は、そのまま
原液として成形に供することができる。また、メタノー
ル、水などで処理して、下記式（ＩＶ）で表される芳香
族ポリアミド−アミド酸
を単離することもできる。(Function) N-silylated aromatic diamine and trimellidic anhydride chloride are reacted in such an organic solvent, and the above-mentioned formula (
The specific method for producing the aromatic polyamide-amic acid derivative represented by n) is not particularly different from the usual low-temperature solution polymerization method. That is, first, after dissolving the N-silylated aromatic diamine in an aprotic organic solvent, it is usually −50 to +
While stirring the solution at about 80"C, preferably from -20 to +50°C, trimellidic anhydride chloride is added either in powder form or in the form of a solution dissolved in an organic solvent, either at -degrees or gradually. Let the reaction occur.The reaction occurs immediately and the viscosity of the reactant increases.Stirring is usually continued for 3 to 244 hours, but in some cases the reaction may be completed within 1 hour.The reaction is completed. The reactant can be directly used as a stock solution for molding.Alternatively, the aromatic polyamide-amic acid represented by the following formula (IV) can be isolated by treatment with methanol, water, etc.
上記−数式（ｎ）および（Ｉ［［）においてポリマーの
重合度ｎを１０〜１００としたのは、ｎが１０以下では
ポリマーとしての十分な性質が発揮できず、又１００以
上ではポリマーの溶解性などに問題が生ずるからである
。The reason why the polymerization degree n of the polymer is set to 10 to 100 in the above formulas (n) and (I This is because problems arise with regard to sexuality, etc.
このようにして得られた上記−数式［１）で表される芳
香族ポリアミド−アミド酸誘導体を従来既知の溶液キャ
スト法などによりフィルムとし、このものを２００ ’
Ｃ以上に加熱するか無水酢酸とピリジンによる化学的処
理を施すことにより、目的とする上記−数式（ＩＩＩ）
で表される芳香族ポリアミド−イミド樹脂へ変換できる
。もちろん、上記−数式（ＩＩ）で表される芳香族ポリ
アミド−アミド酸誘導体から得られる上記−数式（ＩＶ
）で表される芳香族ポリアミド−アミド酸からも、加熱
処理もしくは化学的処理により上記−数式（ＩＩＩ）で
表される芳香族ポリアミド−イミド樹脂を得ることがで
きる。The aromatic polyamide-amic acid derivative represented by the above-mentioned formula [1] thus obtained was formed into a film by a conventionally known solution casting method, etc.
By heating above C or chemically treating with acetic anhydride and pyridine, the desired above-formula (III) can be obtained.
It can be converted into an aromatic polyamide-imide resin represented by Of course, the above-mentioned formula (IV) obtained from the aromatic polyamide-amic acid derivative represented by the above-mentioned formula (II)
) The aromatic polyamide-imide resin represented by the above-mentioned formula (III) can also be obtained from the aromatic polyamide-amic acid represented by formula (III) by heat treatment or chemical treatment.
（実施例） 以下に実施例によりさらに本発明の詳細な説明する。(Example) The present invention will be further explained in detail by Examples below.
実新ｌ」上
Ｎ、Ｎ’−ビス（トリメチルシリル）−４，４’−ジア
ミノジフエニルエーテル１．７２３ｇ（５，０ｍｍｏｌ
）を、窒素ガス気流下、８．３ ｒｄのジメチルアセト
アミドに溶解し、溶液を一５°Ｃに冷却する。このもの
に無水トリメリド酸クロリド１．０５３ｇ（５，０ｍｍ
ｏｌ）を−度に加えて１時間撹はんした。反応温度を５
０°Ｃにし１２２時間撹んした。反応後、反応溶液に３
０−のジメチルアセトアミドを加え、約半量を５００
ｍのメタノールに投入して白色のポリアミド−アミド酸
を沈澱させた。これをろ別後、室温で１昼夜真空乾燥し
た。1.723 g (5.0 mmol) of N,N'-bis(trimethylsilyl)-4,4'-diaminodiphenyl ether
) is dissolved in 8.3 rd dimethylacetamide under a stream of nitrogen gas, and the solution is cooled to -5°C. To this material, 1.053 g of trimellidic anhydride chloride (5.0 mm
ol) was added to the mixture and stirred for 1 hour. Reaction temperature to 5
The mixture was heated to 0°C and stirred for 122 hours. After the reaction, add 3 to the reaction solution.
Add 0-dimethylacetamide and reduce about half of the amount to 500
of methanol to precipitate white polyamide-amic acid. After filtering this, it was vacuum-dried at room temperature for one day and night.
固有粘度： １．８２ｄｌ／ｇ （Ｎ−メチル−２−
ピロリドン中、０．５ｇ／ ａの濃度、３０°Ｃで測定
）メタノールに投入しなかった半量の溶液をガラス板上
に直接流延し、室温で減圧乾燥した。生成したポリアミ
ド−アミド酸誘導体のフィルムを１００°Ｃで６時間、
１５０°Ｃで６時間、２００°Ｃで１時間、２６０°Ｃ
で２時間熱処理してポリアミド−イミドのフィルムを得
た。Intrinsic viscosity: 1.82 dl/g (N-methyl-2-
(concentration of 0.5 g/a in pyrrolidone, measured at 30 °C) The half of the solution that was not poured into methanol was cast directly onto a glass plate and dried under reduced pressure at room temperature. The produced polyamide-amic acid derivative film was heated at 100°C for 6 hours.
6 hours at 150°C, 1 hour at 200°C, 260°C
A polyamide-imide film was obtained by heat treatment for 2 hours.
赤外吸収スペクトル（ｃｍ−’） ： １７６５．１７
０５．１６５５゜７２０゜
元素分析： （Ｃｚ＋）Ｉ＋ｚＮｚ０４）−として計算
。Infrared absorption spectrum (cm-'): 1765.17
05.1655°720° Elemental analysis: Calculated as (Cz+)I+zNz04)-.
計算値、 Ｃ、７０，７８χ、 Ｈ： ３．４０Ｘ、
Ｎ ： ７．８６２実測値、 Ｃ、７０，３６χ、Ｈ：
３．３７χ、Ｎニア、８５χ熱重量測定法による１０χ
重量減少温度は、空気中で５２５℃、窒素中で５３０℃
であった。Calculated value, C, 70,78χ, H: 3.40X,
N: 7.862 actual value, C, 70,36χ, H:
3.37χ, N near, 85χ 10χ by thermogravimetry
Weight loss temperature is 525℃ in air and 530℃ in nitrogen
Met.
−１１２〜−・ １７
Ｎ、Ｎ’−ビス（トリメチルシリル）−４，４′−ジア
ミノジフェニルエーテルと無水トリメリド酸クロリドと
の反応を、表１に示す反応溶媒を使用したほかは実施例
１と同じ条件で行なった。-112~-.17 The reaction between N,N'-bis(trimethylsilyl)-4,4'-diaminodiphenyl ether and trimellidic anhydride was carried out under the same conditions as in Example 1, except that the reaction solvent shown in Table 1 was used. I did it.
得られたポリアミド−アミド酸の収率とＮ−メチル−２
−ピロリドン中、０．５ｇ／ ａ（１）濃度、３０°Ｃ
で測定した固有粘度とを表１に示す。Yield of polyamide-amic acid obtained and N-methyl-2
- in pyrrolidone, 0.5 g/a(1) concentration, 30 °C
Table 1 shows the intrinsic viscosity measured in Table 1.
表−土
ポリアミド−アミド酸
実施例 溶媒 収率（χ） 固有粘度（ａ／ｇ
）２１．４−ジオキサン ９３ ０．７５３
ベンゼン ９４ ０．５７４ クロロフ
ォルム ９２ ０．５９５ テトラヒドロフ
９００．９４
ラン
６ ニトロベンゼン ９５ １．２１７Ｎ−メ
チル−２−ピ ９９ １．４Ｂロリドン
実Ｊ１１亀
Ｎ、Ｎ’−ビス（トリメチルシリル）−４，４’−ジア
ミノジフェニルメタン１．７１３ｇ（５，０＋＋＋ｍｏ
ｌ）を、窒素ガス気流下８．３１１のＮ−メチル−２−
ピロリドンに溶解し、溶液を一５°Ｃに冷却する。この
ものに無水トリメリド酸クロリド１．０５３ｇ（５，０
ｍｎ＋ｏｌ）を−度に加え１時間撹はんした０反応温度
を５０℃にし１２時間撹はんした。反応後、反応溶液に
３ｏｒＩ１１のＮ−メチル−２−ピロリドンを加え、約
半量を５００ ｒｔｔｌのメタノールに投入して白色の
ポリアミド−アミド酸を沈澱させた。これをろ別後、室
温で１昼夜真空乾燥した。Top-soil polyamide-amic acid examples Solvent Yield (χ) Intrinsic viscosity (a/g
)21.4-Dioxane 93 0.753
Benzene 94 0.574 Chloroform 92 0.595 Tetrahydrof
900.94 Run 6 Nitrobenzene 95 1.217N-methyl-2-pi 99 1.4B Lolidon Seed J11 Kame N,N'-bis(trimethylsilyl)-4,4'-diaminodiphenylmethane 1.713g (5,0+++ mo
l) under a nitrogen gas stream at 8.311 N-methyl-2-
Dissolve in pyrrolidone and cool the solution to -5°C. To this, 1.053 g (5.0 g) of trimellidic anhydride chloride
mn+ol) was added to the solution and stirred for 1 hour.The reaction temperature was raised to 50°C and stirred for 12 hours. After the reaction, 3orI11 of N-methyl-2-pyrrolidone was added to the reaction solution, and about half of it was poured into 500 rttl of methanol to precipitate white polyamide-amic acid. After filtering this, it was vacuum-dried at room temperature for one day and night.
固有粘度： １．４２ｄｌ／ｇ （Ｎ−メチル−２−ピ
ロリドン中、０．５ｇ／ ａの濃度、３０°Ｃで測定）
メタノールに投入しなかった半量の溶液をガラス板上に
直接流延し、室温で減圧乾燥した。生成したポリアミド
−アミド酸誘導体のフィルムを１００°Ｃで６時間、１
５０°Ｃで６時間、２００°Ｃで１時間、２６０℃で２
時間熱処理してポリアミド−イミドのフィルムを得た。Intrinsic viscosity: 1.42 dl/g (measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g/a at 30°C)
Half of the solution that was not added to methanol was directly cast onto a glass plate and dried under reduced pressure at room temperature. The resulting polyamide-amic acid derivative film was heated at 100°C for 6 hours for 1
6 hours at 50°C, 1 hour at 200°C, 2 hours at 260°C
After time heat treatment, a polyamide-imide film was obtained.
赤外吸収スペクトル（ｃ＋ｒ’） ： １７７５．１？
１５．１６７０゜１鳳五工
Ｎ、Ｎ’−ビス（トリメチルシリル）パラフェニレンジ
アミン１ 、２６３ｇ （５、０ｍｍｏ ｌ）を、窒素
ガス気流下８．３１ｄのＮ−メチル−２−とロリドンに
溶解し、溶液を一５℃に冷却する。このものに無水トリ
メリド酸クロリド１ 、０５３ｇ （５、Ｏｍｎ＋ｏ
１）を−度に加えて１時間撹はんした。反応温度を５０
℃にし１２時間撹はんした。反応後、反応溶液に３０Ｉ
Ｉ１１のＮ−メチル−２−ピロリドンを加え、約半量を
５００７のメタノールに投入して白色のポリアミド−ア
ミド酸を沈澱させた。これをろ別後、室温で１昼夜真空
乾燥した。Infrared absorption spectrum (c+r'): 1775.1?
15. 1670°1 Hogoko N,N'-bis(trimethylsilyl)paraphenylenediamine 1, 263 g (5.0 mmol) was dissolved in 8.31 d of N-methyl-2- and lolidone under a nitrogen gas stream. , cool the solution to -5°C. To this, 1,053 g of trimellidic anhydride chloride (5, Omn+o
1) was added to the mixture and stirred for 1 hour. Reaction temperature to 50
℃ and stirred for 12 hours. After the reaction, add 30I to the reaction solution.
N-methyl-2-pyrrolidone of I11 was added and about half of the amount was poured into methanol of 5007 to precipitate white polyamide-amic acid. After filtering this, it was vacuum-dried at room temperature for one day and night.
固有粘度： １．４０ｄｌ／ｇ （Ｎ−メチル−２−ピ
ロリドン中、０．５ｇ／ ａの濃度、３０℃で測定）メ
タノールに投入しなかった半量の溶液をガラス板上に直
接流延し、室温で減圧乾燥した。生成したポリアミド−
アミド酸誘導体のフィルムを１００°Ｃで６時間、１５
０℃で６時間、２００°Ｃで１時間、２６０°Ｃで２時
間熱処理してポリアミド−イミドのフィルムを得た。Intrinsic viscosity: 1.40 dl/g (measured in N-methyl-2-pyrrolidone at a concentration of 0.5 g/a at 30°C) Half of the solution that was not poured into methanol was cast directly onto a glass plate. It was dried under reduced pressure at room temperature. Produced polyamide
A film of amic acid derivative was heated at 100°C for 6 hours, 15
A polyamide-imide film was obtained by heat treatment at 0°C for 6 hours, 200°C for 1 hour, and 260°C for 2 hours.
赤外吸収スペクトル（ｃｍ−’） ： １７７５．１？
１５．１６７５゜（発明の効果）
本発明方法によれば、温和な条件下で容易に高重合度を
意味する高い固有粘度を有する芳香族ポリアミド−アミ
ド酸誘導体を製造することができ、また、反応溶媒の選
択の範囲も広がり、多くの非プロトン性有機溶媒を用い
て芳香族ポリアミド−アミド酸誘導体を製造することが
出来る。さらに、これから高重合度の芳香族ポリアミド
−イミド樹脂を製造することが可能であり、耐熱性の繊
維、フィルム、成形用の素材として有用性が高い。Infrared absorption spectrum (cm-'): 1775.1?
15.1675° (Effects of the Invention) According to the method of the present invention, an aromatic polyamide-amic acid derivative having a high intrinsic viscosity, which means a high degree of polymerization, can be easily produced under mild conditions, and The range of selection of reaction solvents is also expanded, and aromatic polyamide-amic acid derivatives can be produced using many aprotic organic solvents. Furthermore, it is possible to produce an aromatic polyamide-imide resin with a high degree of polymerization from it, and it is highly useful as a material for heat-resistant fibers, films, and molding.
Claims (1)
）＿３（式中、Ａｒはフェニレン、メチレンジフェニレ
ン、オキシジフェニレンよりなる群から選ばれた二価の
芳香族基を示す）で表されるＮ−シリル化芳香族ジアミ
ンと無水トリメリト酸クロリドとを非プロトン性有機溶
媒中で反応させて、一般式 ▲数式、化学式、表等があります▼ （式中、Ａｒはフェニレン、メチレンジフェニレン、オ
キシジフェニレンよりなる群から選ばれた二価の芳香族
基を示し、ｎは１０〜１００の整数を示す）で表される
芳香族ポリアミド−アミド酸誘導体を製造し、引き続い
てイミド化処理することを特徴とする、一般式 ▲数式、化学式、表等があります▼ （式中、Ａｒはフェニレン、メチレンジフェニレン、オ
キシジフェニレンよりなる群から選ばれた二価の芳香族
基を示し、ｎは１０〜１００の整数を示す）で表される
芳香族ポリアミド−イミド樹脂の製造方法。[Claims] 1. General formula (CH_3)_3SiNH-Ar-NHSi(CH_3
)_3 (wherein Ar represents a divalent aromatic group selected from the group consisting of phenylene, methylene diphenylene, and oxydiphenylene) and an N-silylated aromatic diamine and trimellitic anhydride chloride. is reacted in an aprotic organic solvent to form the general formula ▲ mathematical formula, chemical formula, table, etc. ▲Mathematical formula, chemical formula, table, characterized by producing an aromatic polyamide-amic acid derivative represented by the following formula (n represents a group group, n is an integer of 10 to 100), and subsequently imidizing it. etc. ▼ (wherein Ar represents a divalent aromatic group selected from the group consisting of phenylene, methylene diphenylene, and oxydiphenylene, and n represents an integer from 10 to 100) A method for producing a group polyamide-imide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28197987A JPH01123832A (en) | 1987-11-10 | 1987-11-10 | Production of aromatic polyamide-imide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28197987A JPH01123832A (en) | 1987-11-10 | 1987-11-10 | Production of aromatic polyamide-imide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01123832A true JPH01123832A (en) | 1989-05-16 |
| JPH0459334B2 JPH0459334B2 (en) | 1992-09-22 |
Family
ID=17646560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28197987A Granted JPH01123832A (en) | 1987-11-10 | 1987-11-10 | Production of aromatic polyamide-imide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01123832A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206124A (en) * | 1991-02-14 | 1993-04-27 | Konica Corporation | Light-sensitive silver halide color photographic material |
| CN105017534A (en) * | 2015-08-13 | 2015-11-04 | 中国科学院光电技术研究所 | Preparation method of soluble colorless transparent low-thermal expansion coefficient polyamide-imide film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4552202B2 (en) * | 2006-06-06 | 2010-09-29 | 株式会社ニコン | Surface inspection device |
-
1987
- 1987-11-10 JP JP28197987A patent/JPH01123832A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206124A (en) * | 1991-02-14 | 1993-04-27 | Konica Corporation | Light-sensitive silver halide color photographic material |
| CN105017534A (en) * | 2015-08-13 | 2015-11-04 | 中国科学院光电技术研究所 | Preparation method of soluble colorless transparent low-thermal expansion coefficient polyamide-imide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0459334B2 (en) | 1992-09-22 |
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