JP2614513B2 - Manufacturing method of polyamide-imide resin - Google Patents
Manufacturing method of polyamide-imide resinInfo
- Publication number
- JP2614513B2 JP2614513B2 JP11755689A JP11755689A JP2614513B2 JP 2614513 B2 JP2614513 B2 JP 2614513B2 JP 11755689 A JP11755689 A JP 11755689A JP 11755689 A JP11755689 A JP 11755689A JP 2614513 B2 JP2614513 B2 JP 2614513B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyamide
- mmol
- resins
- resin
- 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 - Fee Related
Links
- 239000011347 resin Substances 0.000 title description 30
- 229920005989 resin Polymers 0.000 title description 30
- 239000004962 Polyamide-imide Substances 0.000 title description 24
- 229920002312 polyamide-imide Polymers 0.000 title description 24
- 238000004519 manufacturing process Methods 0.000 title description 2
- -1 2-methyl-1,3-phenylene Chemical group 0.000 claims description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 9
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920006122 polyamide resin Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 238000007363 ring formation reaction Methods 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- SKECUWVUULHIJG-UHFFFAOYSA-N 1-n,3-n-bis(3-aminophenyl)-5-hydroxybenzene-1,3-dicarboxamide Chemical compound NC1=CC=CC(NC(=O)C=2C=C(C=C(O)C=2)C(=O)NC=2C=C(N)C=CC=2)=C1 SKECUWVUULHIJG-UHFFFAOYSA-N 0.000 description 4
- QKZZKMWKLMMJFN-UHFFFAOYSA-N 1-n,3-n-bis(4-aminophenyl)-5-hydroxybenzene-1,3-dicarboxamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC(O)=CC(C(=O)NC=2C=CC(N)=CC=2)=C1 QKZZKMWKLMMJFN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- DAKUZVFMMZMWMT-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxamide Chemical compound NC(=O)C1=CC(O)=CC(C(N)=O)=C1 DAKUZVFMMZMWMT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IDGCNCRMTKNJAD-UHFFFAOYSA-N NC=1C(=C(C=CC1)NC(C1=CC(C(=O)NC2=C(C(=CC=C2)N)C)=CC(=C1)O)=O)C Chemical compound NC=1C(=C(C=CC1)NC(C1=CC(C(=O)NC2=C(C(=CC=C2)N)C)=CC(=C1)O)=O)C IDGCNCRMTKNJAD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規なポリアミドイミド樹脂の製造法に関
する。Description: TECHNICAL FIELD The present invention relates to a method for producing a novel polyamide-imide resin.
ポリイミド樹脂、ポリアミド樹脂は、耐熱性をはじめ
とする優れた特性を生かして、多くの分野で例えばフイ
ルム、電線被覆、接着剤、塗料、積層品等に使用されて
いる。また一方ではこれらの特性を生かしつつ、その汎
用性を広げるために、ポリアミドイミド樹脂、ポリエス
テルイミド樹脂、ポリエーテルイミド樹脂等の開発が広
く進められている。BACKGROUND ART Polyimide resins and polyamide resins are used in many fields, for example, for films, electric wire coatings, adhesives, paints, laminates, etc., by taking advantage of excellent properties such as heat resistance. On the other hand, polyamide-imide resins, polyester-imide resins, polyether-imide resins, and the like have been widely developed in order to expand their versatility while utilizing these characteristics.
しかし、現在汎用されているポリイミド樹脂、ポリア
ミド樹脂、ポリアミドイミド樹脂等は、耐熱性は良好で
あるが、成形性等に難点がある。そこで、これらの長
所、短所のバランスをとるために他の反応性樹脂等とポ
リイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂
等との複合化が検討されているが、まだ不十分である。
その主な障害は、これらポリイミド樹脂、ポリアミド樹
脂、ポリアミドイミド樹脂の溶媒溶解性が不十分である
こと、及びこれらポリイミド樹脂、ポリアミド樹脂、ポ
リアミドイミド樹脂と他の反応性樹脂とが所望の組成で
均一に混合しないこと、そのため期待する特性が発現し
ないことにあつた。However, polyimide resins, polyamide resins, polyamide-imide resins, and the like, which are currently widely used, have good heat resistance, but have drawbacks in moldability and the like. Therefore, in order to balance these advantages and disadvantages, the compounding of a polyimide resin, a polyamide resin, a polyamideimide resin, or the like with another reactive resin or the like has been studied, but it is still insufficient.
The main obstacle is that these polyimide resins, polyamide resins, polyamideimide resins have insufficient solvent solubility, and these polyimide resins, polyamide resins, polyamideimide resins and other reactive resins have a desired composition. They did not mix uniformly and therefore did not exhibit the expected properties.
したがつて本発明の目的は、有機溶媒に溶解可能で、
他の反応性樹脂に対する反応性活性点を有し、他の反応
性樹脂と複合化可能なポリアミドイミド樹脂を提供する
ことにある。Therefore, an object of the present invention is to dissolve in an organic solvent,
It is an object of the present invention to provide a polyamideimide resin having a reactive active site for another reactive resin and capable of being complexed with another reactive resin.
本発明は、一般式 （式中Ｒはメタフェニレン基、パラフェニレン基または
２−メチル−1,3−フェニレン基を示す）で表されるジ
アミン化合物を一般式 （式中Arは基 を示し、ここにＷは直接結合または−CO−を示す）で表
されるテトラカルボン酸二無水物と重縮合反応させるこ
とを特徴とするポリアミドイミド樹脂の製造法である。The present invention has the general formula (Wherein R represents a metaphenylene group, a paraphenylene group or a 2-methyl-1,3-phenylene group). (Where Ar is a group Wherein W represents a direct bond or —CO—) and a polycondensation reaction with a tetracarboxylic dianhydride represented by the following formula:
本発明はさらに、式Ｉの化合物および一般式 H2N−R2−NH2 （III） （式中R2はメタフェニレン基、パラフェニレン基、C4ア
ルキレン基、C6アルキレン基またはC7アルキレン基を示
す）で表される化合物を式IIの化合物と重縮合反応させ
ることを特徴とするポリアミド樹脂の製造法である。The invention further relates to a compound of the formula I and a compound of the general formula H 2 N—R 2 —NH 2 (III) wherein R 2 is a metaphenylene group, a paraphenylene group, a C 4 alkylene group, a C 6 alkylene group or a C 7 alkylene group. A polycondensation reaction of a compound of the formula (II) with a compound of the formula II).
本発明に用いられる式Ｉの化合物としては、N,N′−
ビス（３−または４−アミノフェニル）−５−ヒドロキ
シイソフタルアミド、N,N′−ビス（３−アミノ−２−
メチルフェニル）−５−ヒドロキシイソフタルアミド等
があげられる。Compounds of formula I used in the present invention include N, N'-
Bis (3- or 4-aminophenyl) -5-hydroxyisophthalamide, N, N'-bis (3-amino-2-
Methylphenyl) -5-hydroxyisophthalamide and the like.
式IIのテトラカルボン酸二無水物としては、ピロメリ
ット酸二無水物、3,4,3′,4′−ビフェニルテトラカル
ボン酸二無水物、3,4,3′,4′−ベンゾフェノンテトラ
カルボン酸二無水物等があげられる。As the tetracarboxylic dianhydride of the formula II, pyromellitic dianhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-benzophenone tetracarboxylic acid Acid dianhydride and the like.
式IIIの化合物としては、メタまたはパラフェニレン
ジアミン、ヘキサメチレンジアミン、ヘプタメチレンジ
アミン、テトラメチレンジアミン等があげられる。Compounds of formula III include meta or para phenylenediamine, hexamethylene diamine, heptamethylene diamine, tetramethylene diamine, and the like.
ジアミン化合物（Ｉ）やジアミン化合物（III）とテ
トラカルボン酸二無水物誘導体との反応は、公知の方法
を用いて行うことができる。例えば不活性極性有機溶媒
中で、ジアミン１当量に対してテトラカルボン酸二無水
物を0.8〜1.3当量配合し、−20〜150℃好ましくは０〜6
0℃の温度で数十分間ないし数日間反応させ、ポリアミ
ツク酸を生成させ、更にイミド化することにより本発明
のポリアミドイミド樹脂を製造できる。The reaction between the diamine compound (I) or the diamine compound (III) and the tetracarboxylic dianhydride derivative can be carried out using a known method. For example, in an inert polar organic solvent, 0.8 to 1.3 equivalents of tetracarboxylic dianhydride is blended with respect to 1 equivalent of diamine, and -20 to 150 ° C., preferably 0 to 6
The polyamide-imide resin of the present invention can be produced by reacting at a temperature of 0 ° C. for several tens of minutes to several days to generate polyamic acid and further imidization.
不活性極性有機溶媒としては、例えばN,N−ジメチル
ホルムアミド、N,N−ジメチルアセトアミド、Ｎ−メチ
ル−２−ピロリドン、Ｎ−メチルカプロラクタム、ジメ
チルスルホキシド、テトラメチル尿素、ピリジン、ジメ
チルスルホン、ヘキサメチルリン酸トリアミン等があげ
られる。As the inert polar organic solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethyl Triamine phosphate and the like.
イミド化の方法としては、加熱により脱水閉環させる
方法及び脱水閉環触媒を用いて化学的に閉環させる方法
があげられる。Examples of the imidation method include a method of dehydrating a ring by heating and a method of chemically closing a ring using a dehydration catalyst.
加熱により脱水閉環させる場合、反応温度は150〜400
℃好ましくは180〜350℃であり、反応時間は30秒間ない
し10時間好ましくは５分間ないし５時間である。When the ring is dehydrated by heating, the reaction temperature is 150 to 400.
C., preferably 180 to 350.degree. C., and the reaction time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours.
また脱水閉環触媒を用いる場合、反応温度は０〜180
℃好ましくは10〜80℃であり、反応時間は数十分間ない
し数日間好ましくは２〜12時間である。脱水閉環触媒と
しては酢酸、プロピオン酸、酪酸、安息香酸等があげら
れる。環化反応を促進する化合物例えばピリジンを併用
することが好ましい。脱水閉環触媒の使用量は、ジアミ
ンの総量に対して200モル％以上好ましくは300〜1000モ
ル％である。環化反応を促進する化合物の使用量は、ジ
アミンの総量に対して150〜500モル％である。When a dehydration ring-closing catalyst is used, the reaction temperature is 0 to 180.
C., preferably from 10 to 80.degree. C., and the reaction time is from tens of minutes to several days, preferably from 2 to 12 hours. Examples of the dehydration ring-closing catalyst include acetic acid, propionic acid, butyric acid, and benzoic acid. It is preferable to use a compound that promotes the cyclization reaction, for example, pyridine. The amount of the dehydration ring-closing catalyst used is 200 mol% or more, preferably 300 to 1000 mol%, based on the total amount of the diamine. The amount of the compound that promotes the cyclization reaction is 150 to 500 mol% based on the total amount of the diamine.
本発明のポリアミドイミド樹脂は、固有粘度（Ｎ−メ
チル−２−ピロリドン中、0.5g/dl濃度、30℃）が0.1〜
5.0dl/g好ましくは0.2〜1.5dl/gである。The polyamideimide resin of the present invention has an intrinsic viscosity (in N-methyl-2-pyrrolidone, 0.5 g / dl concentration, 30 ° C.) of 0.1 to 0.1.
5.0 dl / g, preferably 0.2 to 1.5 dl / g.
本発明により得られたポリアミドイミド樹脂は、耐熱
性、溶媒溶解性に優れ、他の反応性樹脂と均一に混合す
ることができる。本発明のポリアミドイミド樹脂は、高
温で使用するフイルム、電線被覆、接着剤、塗料、積層
品等の素材として有用である。The polyamideimide resin obtained according to the present invention has excellent heat resistance and solvent solubility, and can be uniformly mixed with other reactive resins. The polyamide-imide resin of the present invention is useful as a material for films, electric wire coatings, adhesives, paints, laminates, and the like used at high temperatures.
実施例１ N,N′−ビス（３−アミノフエニル）−５−ヒドロキ
シイソフタルアミド18g（50ミリモル）と3,4,3′,4′−
ベンゾフエノンテトラカルボン酸二無水物16g（50ミリ
モル）をＮ−メチル−２−ピロリドン150mlに溶解し、
窒素雰囲気下、室温で６時間反応させて、ポリアミツク
酸溶液を得た。このポリアミツク酸溶液を200℃で２時
間加熱し、脱水環化反応を行つた。放冷後、重合体溶液
を、大量のメタノール中に注ぎ入れた。析出した固体を
別し、過物を洗浄、乾燥し、固有粘度0.65dl/g（Ｎ
−メチル−２−ピロリドン中、0.5g/dl濃度、30℃で測
定、以下同じ）の重合体を得た。Example 1 18 g (50 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide and 3,4,3 ', 4'-
Dissolve 16 g (50 mmol) of benzophenonetetracarboxylic dianhydride in 150 ml of N-methyl-2-pyrrolidone,
The mixture was reacted at room temperature for 6 hours in a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated, the excess was washed and dried, and the intrinsic viscosity was 0.65 dl / g (N
-Methyl-2-pyrrolidone at a concentration of 0.5 g / dl, measured at 30 ° C, the same applies hereinafter).
赤外線スペクトル分析により3227cm-1にフエノール性
水酸基の吸収、1724cm-1及び1779cm-1にイミド結合によ
る吸収、1677cm-1にアミド結合によるカルボニル基の吸
収が認められた。これらの結果より、このものは第１表
に示す繰り返し単位を有するポリアミドイミドであるこ
とが確認された。Absorption of phenolic hydroxyl groups to 3227cm -1 by infrared spectrum analysis, absorption by imide bond to 1724 cm -1 and 1779cm -1, absorption of a carbonyl group by an amide bond to 1677cm -1 were observed. From these results, it was confirmed that this was a polyamide imide having a repeating unit shown in Table 1.
実施例２ N,N′−ビス（３−アミノフエニル）−５−ヒドロキ
シイソフタルアミドに代えてN,N′−ビス（４−アミノ
フエニル）−５−ヒドロキシイソフタルアミド18g（50
ミリモル）を用い、その他は実施例１と同様に操作し、
固有粘度0.58dl/gのポリアミドイミド樹脂を得た。Example 2 18 g of N, N'-bis (4-aminophenyl) -5-hydroxyisophthalamide instead of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide
Mmol), and the other operations were the same as in Example 1.
A polyamideimide resin having an intrinsic viscosity of 0.58 dl / g was obtained.
実施例３ 3,4,3′,4′−ベンゾフエノンテトラカルボン酸二無
水物に代えてピロメリツト酸二無水物11g（50ミリモ
ル）を用い、その他は実施例１と同様に操作し、固有粘
度0.49dl/gのポリアミドイミド樹脂を得た。Example 3 In place of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 11 g (50 mmol) of pyromellitic dianhydride was used. A polyamideimide resin having a viscosity of 0.49 dl / g was obtained.
実施例４ N,N′−ビス（４−アミノフエニル）−５−ヒドロキ
シイソフタルアミド18g（50ミリモル）及びピロメリツ
ト酸二無水物11g（50ミリモル）を用い、実施例１と同
様に操作し、固有粘度0.51dl/gのポリアミドイミド樹脂
を得た。Example 4 The same operation as in Example 1 was carried out using 18 g (50 mmol) of N, N'-bis (4-aminophenyl) -5-hydroxyisophthalamide and 11 g (50 mmol) of pyromellitic dianhydride to obtain an intrinsic viscosity. A polyamide imide resin of 0.51 dl / g was obtained.
実施例５ 3,4,3′,4′−ベンゾフエノンテトラカルボン酸二無
水物に代えて4,4′−ビフタル酸二無水物15g（50ミリモ
ル）を用い、その他は実施例１と同様に操作し、固有粘
度0.68dl/gのポリアミドイミド樹脂を得た。Example 5 Same as Example 1 except that 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride was replaced by 15 g (50 mmol) of 4,4'-biphthalic dianhydride To obtain a polyamide-imide resin having an intrinsic viscosity of 0.68 dl / g.
実施例６ N,N′−ビス（４−アミノフエニル）−５−ヒドロキ
シイソフタルアミド18g（50ミリモル）及び4,4′−ビフ
タル酸二無水物15g（50ミリモル）を用い、実施例１と
同様に操作し、固有粘度0.60dl/gのポリアミドイミド樹
脂を得た。Example 6 As in Example 1, using 18 g (50 mmol) of N, N'-bis (4-aminophenyl) -5-hydroxyisophthalamide and 15 g (50 mmol) of 4,4'-biphthalic dianhydride. By operation, a polyamideimide resin having an intrinsic viscosity of 0.60 dl / g was obtained.
実施例７ N,N′−ビス（４−アミノフエニル）−５−ヒドロキ
シイソフタルアミドに代えてN,N′−ビス（３−アミノ
−２−メチルフエニル）−５−ヒドロキシイソフタルア
ミド19.5g（50ミリモル）を用い、その他は実施例１と
同様に操作し、固有粘度0.46dl/gのポリアミドイミド樹
脂を得た。Example 7 19.5 g (50 mmol) of N, N'-bis (3-amino-2-methylphenyl) -5-hydroxyisophthalamide in place of N, N'-bis (4-aminophenyl) -5-hydroxyisophthalamide Using the same procedures as in Example 1 to obtain a polyamide-imide resin having an intrinsic viscosity of 0.46 dl / g.
実施例８ N,N′−ビス（３−アミノ−２−メチルフエニル）−
５−ヒドロキシイソフタルアミド19.5g（50ミリモル）
及びピロメリツト酸二無水物11g（50ミリモル）を用
い、実施例１と同様に操作し、固有粘度0.49dl/gのポリ
アミドイミド樹脂を得た。Example 8 N, N'-bis (3-amino-2-methylphenyl)-
19.5 g (50 mmol) of 5-hydroxyisophthalamide
And 11 g (50 mmol) of pyromellitic dianhydride and the same operation as in Example 1 to obtain a polyamideimide resin having an intrinsic viscosity of 0.49 dl / g.
実施例９ N,N′−ビス（３−アミノ−２−メチルフエニル）−
５−ヒドロキシイソフタルアミド19.5g（50ミリモル）
及び4,4′−ビフタル酸二無水物15g（50ミリモル）を用
い、実施例１と同様に操作し、固有粘度0.49dl/gのポリ
アミドイミド樹脂を得た。Example 9 N, N'-bis (3-amino-2-methylphenyl)-
19.5 g (50 mmol) of 5-hydroxyisophthalamide
Using 15 g (50 mmol) of 4,4'-biphthalic dianhydride and the same procedure as in Example 1, a polyamideimide resin having an intrinsic viscosity of 0.49 dl / g was obtained.
実施例10 N,N′−ビス（３−アミノフエニル）−５−ヒドロキ
シイソフタルアミド14.5g（40ミリモル）とｍ−フエニ
レンジアミン1.1g（10ミリモル）と3,4,3′,4′−ベン
ゾフエノンテトラカルボン酸二無水物16g（50ミリモ
ル）をＮ−メチル−２−ピロリドン150mlに溶解し、窒
素雰囲気下、室温で６時間反応させて、ポリアミツク酸
溶液を得た。このポリアミツク酸溶液を200℃で２時間
加熱し、脱水環化反応を行つた。放冷後、重合体溶液
を、大量のメタノール中に注ぎ入れた。析出した固体を
別し、過物を洗浄、乾燥し、固有粘度0.55dl/gのポ
リアミドイミド樹脂を得た。Example 10 14.5 g (40 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide, 1.1 g (10 mmol) of m-phenylenediamine and 3,4,3 ', 4'-benzo 16 g (50 mmol) of phenonetetracarboxylic dianhydride was dissolved in 150 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours under a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated, and the excess was washed and dried to obtain a polyamideimide resin having an intrinsic viscosity of 0.55 dl / g.
実施例11 N,N′−ビス（３−アミノフエニル）−５−ヒドロキ
シイソフタルアミド14.5g（40ミリモル）とヘキサメチ
レンジアミン1.2g（10ミリモル）と3,4,3′,4′−ベン
ゾフエノンテトラカルボン酸二無水物16g（50ミリモ
ル）をＮ−メチル−２−ピロリドン150mlに溶解し、窒
素雰囲気下、室温で６時間反応させて、ポリアミツク酸
溶液を得た。このポリアミツク酸溶液を200℃で２時間
加熱し、脱水環化反応を行つた。放冷後、重合体溶液
を、大量のメタノール中に注ぎ入れた。析出した固体を
別し、過物を洗浄、乾燥し、固有粘度0.52dl/gのポ
リアミドイミド樹脂を得た。Example 11 14.5 g (40 mmol) of N, N'-bis (3-aminophenyl) -5-hydroxyisophthalamide, 1.2 g (10 mmol) of hexamethylenediamine and 3,4,3 ', 4'-benzophenone 16 g (50 mmol) of tetracarboxylic dianhydride was dissolved in 150 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours under a nitrogen atmosphere to obtain a polyamic acid solution. This polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After cooling, the polymer solution was poured into a large amount of methanol. The precipitated solid was separated, and the excess was washed and dried to obtain a polyamideimide resin having an intrinsic viscosity of 0.52 dl / g.
実施例１〜11で得られたポリアミドイミド樹脂の繰り
返し単位を下記に示す。なお式中のＺは を示す。The repeating units of the polyamide-imide resins obtained in Examples 1 to 11 are shown below. Note that Z in the formula is Is shown.
Claims (2)
２−メチル−1,3−フェニレン基を示す）で表されるジ
アミン化合物を一般式 （式中Arは基 を示し、ここにＷは直接結合または−CO−を示す）で表
されるテトラカルボン酸二無水物と重縮合反応させるこ
とを特徴とするポリアミドイミド樹脂の製造法。(1) General formula (Wherein R represents a metaphenylene group, a paraphenylene group or a 2-methyl-1,3-phenylene group). (Where Ar is a group Wherein W represents a direct bond or —CO—) and a polycondensation reaction with a tetracarboxylic dianhydride represented by the following formula:
２−メチル−1,3−フェニレン基を示す）で表されるジ
アミン化合物及び一般式 H2N−R2−NH2 （III） （式中R2はメタフェニレン基、パラフェニレン基、C4ア
ルキレン基、C6アルキレン基またはC7アルキレン基を示
す）で表される化合物を一般式 （式中Arは基 を示し、ここにＷは直接結合または−CO−を示す）で表
されるテトラカルボン酸二無水物と重縮合反応させるこ
とを特徴とするポリアミドイミド樹脂の製造法。2. General formula General formula (Wherein R represents a metaphenylene group, a paraphenylene group or a 2-methyl-1,3-phenylene group) and a general formula H 2 N—R 2 —NH 2 (III) R 2 represents a metaphenylene group, a paraphenylene group, a C 4 alkylene group, a C 6 alkylene group or a C 7 alkylene group) (Where Ar is a group Wherein W represents a direct bond or —CO—) and a polycondensation reaction with a tetracarboxylic dianhydride represented by the following formula:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11755689A JP2614513B2 (en) | 1989-05-12 | 1989-05-12 | Manufacturing method of polyamide-imide resin |
| EP90302623A EP0387106B1 (en) | 1989-03-10 | 1990-03-12 | Novel diamine compounds, production of the same and polyamideimide resins produced therefrom |
| DE69006377T DE69006377T2 (en) | 1989-03-10 | 1990-03-12 | Diamine compounds, their preparation and polyamideimide resins produced therefrom. |
| US07/491,988 US5019642A (en) | 1989-03-10 | 1990-03-12 | Novel diamine compounds, production of the same and polyamideimide resins produced therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11755689A JP2614513B2 (en) | 1989-05-12 | 1989-05-12 | Manufacturing method of polyamide-imide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02298513A JPH02298513A (en) | 1990-12-10 |
| JP2614513B2 true JP2614513B2 (en) | 1997-05-28 |
Family
ID=14714741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11755689A Expired - Fee Related JP2614513B2 (en) | 1989-03-10 | 1989-05-12 | Manufacturing method of polyamide-imide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2614513B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2814403B2 (en) | 1989-11-28 | 1998-10-22 | 株式会社巴川製紙所 | Method for producing polyamide-imide copolymer |
-
1989
- 1989-05-12 JP JP11755689A patent/JP2614513B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2814403B2 (en) | 1989-11-28 | 1998-10-22 | 株式会社巴川製紙所 | Method for producing polyamide-imide copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02298513A (en) | 1990-12-10 |
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