JPS648013B2 - - Google Patents
Info
- Publication number
- JPS648013B2 JPS648013B2 JP11401579A JP11401579A JPS648013B2 JP S648013 B2 JPS648013 B2 JP S648013B2 JP 11401579 A JP11401579 A JP 11401579A JP 11401579 A JP11401579 A JP 11401579A JP S648013 B2 JPS648013 B2 JP S648013B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyamide
- cresol
- acid
- imide
- 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
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 239000004962 Polyamide-imide Substances 0.000 claims description 18
- 229920002312 polyamide-imide Polymers 0.000 claims description 18
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 16
- -1 aromatic tricarboxylic acid Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 125000005590 trimellitic acid group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 9
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
- 229930003836 cresol Natural products 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 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
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000006838 isophorone group Chemical group 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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)
Description
本発明は、新規なポリアミドイミド樹脂と、そ
の製造方法に関するものであり、更に詳しくは、
有機溶剤に可溶性の電線被覆、フイルム加工など
に使用される耐熱性の新規な芳香族ポリアミドイ
ミド樹脂とその製造方法に関するものである。
従来、これらの用途に使用される耐熱性重合体
としては、ポリイミド系重合体、ポリアミドイミ
ド系重合体が既に知られている。ポリイミド系重
合体は、一般に有機溶媒に不溶のため、電線被
覆、フイルム加工においてはポリアミド酸の形で
成形加工した後、次いで加熱等の方法により、脱
水閉環させてポリイミドとし、使用されるのが普
通であり、ポリアミド酸の保存安定性と溶媒不溶
性及び溶融成形性が困難なため加工時の作業性が
悪いという本質的な問題点を有している。又市販
のポリアミドイミド樹脂はポリイミド系重合体に
比べて、比較的有機溶剤への溶解性にすぐれてい
るが、高価で吸水性の極性溶剤にしか溶解せず、
安価で吸水性がないため取り扱いの容易なクレゾ
ール系溶剤などには溶解しない。
本発明者等は、かかる考えのもとに、研究を進
めたところ、特定の構造をもつジアミンを芳香族
トリカルボン酸又はその誘導体で類似の機能を有
する化合物とを、一定の条件のもとに、有機溶剤
中で反応させれば、電気特性、耐熱性、機械的性
質に優れた、有機溶剤特にクレゾール系溶剤に可
溶性のポリアミドイミド樹脂が生成することを見
い出し、本発明に到達した。
本発明は、下記化学構造式からなる有機溶剤に
可溶性の新規な芳香族ポリアミドイミド樹脂に関
するものである。
（式中、Ｒは炭素数６〜20の８価の芳香族基、ｎ
は繰り返し単位を表わす整数であり、該樹脂の25
重量％のｍ−クレゾール中の25℃における溶液粘
度が500〜10000cpsである。）
本発明は、又、上記化学構造式を有する芳香族
ポリアミドイミド樹脂の新規な製造法をも提供す
るものである。
本発明では、イソホロン構造
The present invention relates to a novel polyamideimide resin and a method for producing the same, and more specifically,
The present invention relates to a new heat-resistant aromatic polyamide-imide resin that is soluble in organic solvents and is used for electric wire coating, film processing, etc., and a method for producing the same. Conventionally, polyimide-based polymers and polyamide-imide-based polymers are already known as heat-resistant polymers used for these purposes. Polyimide polymers are generally insoluble in organic solvents, so for wire coating and film processing, they are first molded in the form of polyamic acid, and then dehydrated and ring-closed using methods such as heating to form polyimide. However, it has the essential problem of poor workability during processing due to the storage stability, solvent insolubility, and melt moldability of polyamic acid. In addition, commercially available polyamide-imide resins have relatively better solubility in organic solvents than polyimide polymers, but they only dissolve in expensive and water-absorbing polar solvents.
It is inexpensive and does not absorb water, so it does not dissolve in easily handled cresol solvents. Based on this idea, the present inventors conducted research and found that a diamine with a specific structure was combined with an aromatic tricarboxylic acid or its derivative having a similar function under certain conditions. It was discovered that a polyamide-imide resin having excellent electrical properties, heat resistance, and mechanical properties and soluble in organic solvents, particularly cresol solvents, can be produced by reacting in an organic solvent, and the present invention was achieved based on this discovery. The present invention relates to a novel aromatic polyamide-imide resin that is soluble in organic solvents and has the chemical structural formula shown below. (In the formula, R is an octavalent aromatic group having 6 to 20 carbon atoms, n
is an integer representing a repeating unit, and 25
The solution viscosity at 25° C. in weight percent m-cresol is 500-10000 cps. ) The present invention also provides a novel method for producing an aromatic polyamideimide resin having the above chemical structural formula. In the present invention, isophorone structure
【式】を有するジアミンを使
用するが、一般に知られている脂肪族ジアミンを
使用した場合に比べ、耐熱性の低下は小さく、し
かも生成する芳香族ポリアミドイミド樹脂を、有
機溶剤特にクレゾール系溶剤に可溶性にすること
を可能にする。
本発明の前記化学構造式を有する芳香族ポリア
ミドイミド樹脂は、芳香族トリカルボン酸又は、
その誘導体で類似の機能を有する化合物と、下記
化学構造式のイソホロンジアミン（３−アミノメ
チル−３，５，５−トリメチルシクロヘキシル−
アミン）とを反応させることにより得られる。
芳香族トリカルボン酸としてはトリメリツト
酸、ジフエニルメタン−３，3′，４−トリカルボ
ン酸、ジフエニルエーテル−３，3′，４−トリカ
ルボン酸、ジフエニルスルホン−３，3′，４−ト
リカルボン酸、ジフエニル−３，3′，４−トリカ
ルボン酸等があげられる。上記芳香族トリカルボ
ン酸の誘導体で類似の機能を有する化合物として
は、それらの酸無水物、エステル化物、アミド化
物等の誘導体が使用されるが、望ましくは、酸無
水物がよい。
更に耐熱性を必要とする用途には芳香族トリカ
ルボン酸又はその機能誘導体の１〜99モル％を芳
香族テトラカルボン酸又はその無水物の99〜１モ
ル％で置き換えて、反応することも可能であり、
耐熱性の更に向上したポリアミドイミド樹脂を製
造することが出来る。１〜50モル％を置き換える
のが特に好ましい。
芳香族テトラカルボン酸としては、ピロメリツ
ト酸、ベンゾフエノンテトラカルボン酸、ナフタ
レン２，３，６，７−テトラカルボン酸、ナフタ
レン１，２，５，６−テトラカルボン酸、３，
3′，４，4′−ジフエニルテトラカルボン酸、２，
２−ビス（３，４−ジカルボキシフエニル）プロ
パンなどがあげられ、又これらの酸無水物も使用
できる。
本発明のポリアミドイミド重合反応は、化学的
に不活性な有機溶剤存在下に実施するのが好まし
いが、例えば、Ｎ−メチルピロリドン、ジメチル
アセトアミド、ジメチルホルムアミド、ジメチル
スルホキシド、ジメチルスルホン、Ｎ−メチルカ
プロラクタム、クレゾール酸、Ｐ−クレゾール、
ｍ−クレゾール等が使用可能である。
一般にクレゾール系溶剤は、他の極性溶剤に比
較して、安価であり、吸水性でないため取り扱い
も容易であるところから、工業的にはクレゾール
系溶剤を使用することが望ましい。又上記溶媒の
混合物、上記溶媒と少量のトルエン、キシレン、
エチルベンゼン等との混合物も使用出来る。
芳香族トリカルボン酸又はその誘導体で類似の
機能を有する化合物と、イソホロンジアミンとの
使用モル比は、当モルが望ましい。しかし、若干
のどちらかの過剰の下でも温度、触媒の種類、
量、圧力等特定の条件を選べば、重合することは
可能である。
本発明は、有機塩基不在下でも実施可能である
が、有機塩基存在下で実施することにより、重合
を促進することが可能である。
有機塩基類は、塩基度としてPKa値8.0以上特
に8.5以上のものであれば、広く選択使用できる。
例えば、第３級アミン、第２級アミンがあげられ
る。更に具体的にはトリエチルアミン、トリブチ
ルアミン、トリエタノールアミン、トリエチレン
ジアミン、ピリジン、キノリン、イソキノリン、
Ｎ−テトラメチルエチレンジアミン、ジブチルア
ミン、ジエタノールアミン、ピペリジン、メチル
シクロヘキシルアミン、モルフオリン等があげら
れる。
重合温度は、50℃〜300℃好ましくは、100℃〜
250℃の温度範囲を選択するのが望ましい。
本発明の方法によつて得られる芳香族ポリアミ
ドイミド樹脂は、有機極性溶剤に可溶性であり特
にクレゾール系溶剤を反応溶媒に使用した場合に
は、重合溶液の形でコイル含浸ワニス、ワイヤエ
ナメル、ワニスクロス類等の電気絶縁用ワニスと
して用いられる。又樹脂溶液から、耐熱性と機械
的強度の優れたフイルムを製造することができ、
各種応用分野に利用することができる。
以下実施例により、本発明を具体的に説明する
が、本発明はこれらの実施例により限定されるも
のではない。
実施例 １
撹拌機、温度計、冷却管及び窒素導入管のつい
た500ml四つ口フラスコに、トリメリツト酸無水
物19.2ｇ（0.1モル）とｍ−クレゾール94mlを加
え、溶解した。
次にイソホロンジアミン17.0ｇ（0.1モル）を
加え、温度を160℃に昇温したところ、生成水を
留出しながら増粘した。１時間後220℃に昇温し
24時間加熱撹拌した。
得られた溶液は、暗赤色の溶液で、20℃で溶液
粘度を測定したところ、750cpsであつた。
実施例 ２
実施例１と同様の装置、方法で、トリメリツト
酸無水物19.2ｇ（0.1モル）、ｍ−クレゾール94
ml、イソホロンジアミン17.0ｇ（0.1モル）を加
え溶解したのち、トリエチレンジアミン0.14ｇ
（1.25ミリモル）を添加して温度を160℃に昇温し
た。ゆつくり、生成水を留出しながら増粘した
後、220℃に昇温し、12時間加熱撹拌を行つた。
得られた溶液は、透明な赤色の粘稠な溶液で、20
℃で粘度を測定したところ、3000cpsであつた。
次に生成した樹脂の赤外スペクトルを測定したと
ころ、図−１の様なスペクトルを示し、特にイミ
ド環の特性吸収帯である1770cm-1とアミド結合の
1720〜1700cm-1に顕著な吸収を示し、その他の吸
収を解析した結果、下式のような、ほぼ完全に閉
環したイミド構造を有するポリアミドイミド構造
であることが確認された。
実施例 ３〜７
実施例１と同様の装置方法で、ポリアミドイミ
ド樹脂を得た。
原料、反応条件等を第１表に示す。Although a diamine having the following formula is used, the decrease in heat resistance is smaller than when using generally known aliphatic diamines, and the resulting aromatic polyamide-imide resin can be easily used in organic solvents, especially cresol solvents. Allows to be made soluble. The aromatic polyamideimide resin having the chemical structural formula of the present invention is an aromatic tricarboxylic acid or
Compounds with similar functions as derivatives thereof and isophoronediamine (3-aminomethyl-3,5,5-trimethylcyclohexyl-
amine). Aromatic tricarboxylic acids include trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ether-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-tricarboxylic acid, diphenyl Examples include -3,3',4-tricarboxylic acid. As the derivatives of the above-mentioned aromatic tricarboxylic acids having similar functions, derivatives such as acid anhydrides, esters, and amides thereof are used, and acid anhydrides are preferable. Furthermore, for applications requiring heat resistance, it is also possible to react by replacing 1 to 99 mol% of aromatic tricarboxylic acid or its functional derivative with 99 to 1 mol% of aromatic tetracarboxylic acid or its anhydride. can be,
A polyamide-imide resin with further improved heat resistance can be produced. Particular preference is given to replacing 1 to 50 mol%. Aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, naphthalene 2,3,6,7-tetracarboxylic acid, naphthalene 1,2,5,6-tetracarboxylic acid, 3,
3',4,4'-diphenyltetracarboxylic acid, 2,
Examples include 2-bis(3,4-dicarboxyphenyl)propane, and acid anhydrides thereof can also be used. The polyamideimide polymerization reaction of the present invention is preferably carried out in the presence of a chemically inert organic solvent, such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide, dimethylsulfone, N-methylcaprolactam. , cresylic acid, P-cresol,
m-cresol etc. can be used. In general, cresol solvents are less expensive than other polar solvents, and since they are not water-absorbing, they are easy to handle, so it is desirable to use cresol solvents from an industrial perspective. Also, a mixture of the above solvents, the above solvents and a small amount of toluene, xylene,
A mixture with ethylbenzene etc. can also be used. The molar ratio of aromatic tricarboxylic acid or its derivative having a similar function to isophorone diamine is preferably equimolar. However, even under slight excess of either temperature, catalyst type,
Polymerization is possible if specific conditions such as amount and pressure are selected. Although the present invention can be carried out in the absence of an organic base, polymerization can be promoted by carrying out the process in the presence of an organic base. Organic bases can be selected from a wide range of basicities as long as they have a PKa value of 8.0 or higher, especially 8.5 or higher.
Examples include tertiary amines and secondary amines. More specifically, triethylamine, tributylamine, triethanolamine, triethylenediamine, pyridine, quinoline, isoquinoline,
Examples include N-tetramethylethylenediamine, dibutylamine, diethanolamine, piperidine, methylcyclohexylamine, and morpholine. Polymerization temperature is 50°C to 300°C, preferably 100°C to
It is desirable to choose a temperature range of 250 °C. The aromatic polyamideimide resin obtained by the method of the present invention is soluble in organic polar solvents, and in particular when a cresol solvent is used as a reaction solvent, it can be used in coil impregnation varnish, wire enamel, varnish, etc. in the form of a polymerization solution. Used as an electrically insulating varnish for cloth, etc. In addition, it is possible to produce films with excellent heat resistance and mechanical strength from resin solutions.
It can be used in various application fields. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 19.2 g (0.1 mol) of trimellitic anhydride and 94 ml of m-cresol were added to a 500 ml four-necked flask equipped with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet tube, and dissolved therein. Next, 17.0 g (0.1 mol) of isophorone diamine was added and the temperature was raised to 160°C, which increased the viscosity while distilling off the produced water. After 1 hour, the temperature was raised to 220℃.
The mixture was heated and stirred for 24 hours. The obtained solution was a dark red solution, and the solution viscosity was measured at 20° C. and found to be 750 cps. Example 2 Using the same equipment and method as in Example 1, 19.2 g (0.1 mol) of trimellitic anhydride and m-cresol 94
After adding and dissolving 17.0 g (0.1 mol) of isophorone diamine, 0.14 g of triethylene diamine
(1.25 mmol) was added and the temperature was raised to 160°C. After the mixture was slowly made and thickened while distilling the produced water, the temperature was raised to 220°C, and the mixture was heated and stirred for 12 hours.
The resulting solution is a clear red viscous solution with 20
When the viscosity was measured at °C, it was 3000 cps.
Next, when we measured the infrared spectrum of the resin produced, it showed a spectrum as shown in Figure 1, especially the characteristic absorption band of the imide ring at 1770 cm -1 and the amide bond.
It showed remarkable absorption at 1720 to 1700 cm -1 , and analysis of other absorptions confirmed that it was a polyamide-imide structure having an almost completely ring-closed imide structure as shown in the formula below. Examples 3 to 7 Polyamide-imide resins were obtained using the same equipment and method as in Example 1. Raw materials, reaction conditions, etc. are shown in Table 1.
【表】
実施例 ８
実施例１及び実施例２と同様の装置、方法でト
リメリツト酸無水物のかわりにトリメリツト酸
21.0ｇ（0.1モル）、ｍ−クレゾール94ml、イソホ
ロンジアミン17.0ｇ（0.1モル）を加え溶解した
後、トリエチレンジアミン0.14ｇ（1.25ミリモ
ル）を添加して温度を160℃に昇温した。ゆつく
り生成水を留出しながら、増粘した後、220℃に
昇温し、12時間加熱撹拌を行つた。
得られた溶液は、透明な赤色の粘稠な溶液で、
20℃で粘度を測定したところ、2500cpsであつた。
次に生成した樹脂の赤外スペクトルを測定したと
ころ、図−１と同様なスペクトルを示し、特にイ
ミド環の特性吸収帯である1770cm-1とアミド結合
の1720〜1700cm-1に顕著な吸収を示し、実施例１
及び実施例２と同一のほぼ完全に閉環したイミド
構造を有するポリアミドイミド構造であることが
確認された。[Table] Example 8 Using the same equipment and method as in Examples 1 and 2, trimellitic acid was added instead of trimellitic anhydride.
After adding and dissolving 21.0 g (0.1 mol) of m-cresol, 94 ml of m-cresol, and 17.0 g (0.1 mol) of isophorone diamine, 0.14 g (1.25 mmol) of triethylenediamine was added and the temperature was raised to 160°C. After increasing the viscosity while slowly distilling the produced water, the temperature was raised to 220°C, and the mixture was heated and stirred for 12 hours. The resulting solution is a clear red viscous solution,
When the viscosity was measured at 20°C, it was 2500 cps.
Next, when we measured the infrared spectrum of the resin produced, it showed a spectrum similar to that shown in Figure 1, with particularly pronounced absorption at 1770 cm -1 , which is the characteristic absorption band of the imide ring, and between 1720 and 1700 cm -1 of the amide bond. Example 1
It was confirmed that the polyamide-imide structure had the same almost completely ring-closed imide structure as in Example 2.
図−１は、実施例２で得られた樹脂の赤外吸収
スペクトルを示す。
Figure 1 shows the infrared absorption spectrum of the resin obtained in Example 2.
Claims (1)
性のポリアミドイミド樹脂であつて、Ｒは炭素数
６〜20の３価の芳香族基、ｎは繰返し単位を表わ
す整数であり、該樹脂の25重量％のｍ−クレゾー
ル中の25℃における溶液粘度が500〜10000cpsで
ある新規ポリアミドイミド樹脂。 ２ 下記の繰返し単位を有する特許請求の範囲第
１項記載のポリアミドイミド樹脂。 （ｎは前記と同じ） ３ 芳香族トリカルボン酸またはその機能性誘導
体とイソホロンジアミンの実質的に等モル量を有
機溶媒中で加熱反応させ、下記の繰返し単位を有
する、有機溶剤に可溶性の新規ポリアミドイミド
樹脂を製造する方法。 （式中、Ｒは炭素数６〜20の３価の芳香族基、ｎ
は繰返し単位を表わす整数であり、該樹脂の25重
量％のｍ−クレゾール中の25℃における溶液粘度
が500〜10000cpsである。） ４ 有機塩基の存在下に加熱反応させる特許請求
の範囲第３項記載の製造方法。 ５ 芳香族トリカルボン酸またはその機能性誘導
体が、トリメリツト酸またはその無水物である特
許請求の範囲第３項記載の製造方法。[Scope of Claims] 1 A polyamide-imide resin soluble in organic solvents having the following repeating units, R is a trivalent aromatic group having 6 to 20 carbon atoms, and n is an integer representing the repeating unit. , a novel polyamideimide resin having a solution viscosity of 500 to 10,000 cps at 25°C in m-cresol containing 25% by weight of the resin. 2. A polyamide-imide resin according to claim 1, which has the following repeating unit. (n is the same as above) 3 Substantially equimolar amounts of aromatic tricarboxylic acid or its functional derivative and isophorone diamine are heated and reacted in an organic solvent to produce a novel polyamide soluble in organic solvents having the following repeating units. A method of producing imide resin. (In the formula, R is a trivalent aromatic group having 6 to 20 carbon atoms, n
is an integer representing a repeating unit, and the solution viscosity of the resin in 25% by weight m-cresol at 25°C is 500 to 10,000 cps. ) 4. The manufacturing method according to claim 3, wherein the reaction is carried out by heating in the presence of an organic base. 5. The manufacturing method according to claim 3, wherein the aromatic tricarboxylic acid or its functional derivative is trimellitic acid or its anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11401579A JPS5638325A (en) | 1979-09-04 | 1979-09-04 | Polyamide-imide resin soluble in organic solvent, and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11401579A JPS5638325A (en) | 1979-09-04 | 1979-09-04 | Polyamide-imide resin soluble in organic solvent, and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5638325A JPS5638325A (en) | 1981-04-13 |
| JPS648013B2 true JPS648013B2 (en) | 1989-02-10 |
Family
ID=14626908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11401579A Granted JPS5638325A (en) | 1979-09-04 | 1979-09-04 | Polyamide-imide resin soluble in organic solvent, and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5638325A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0128814B1 (en) * | 1993-07-05 | 1998-04-07 | 강박광 | Polyamideimide resins containing isophorone diamine strncture |
-
1979
- 1979-09-04 JP JP11401579A patent/JPS5638325A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5638325A (en) | 1981-04-13 |
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