JPS62283124A - Production of polyamide resin - Google Patents
Production of polyamide resinInfo
- Publication number
- JPS62283124A JPS62283124A JP12515386A JP12515386A JPS62283124A JP S62283124 A JPS62283124 A JP S62283124A JP 12515386 A JP12515386 A JP 12515386A JP 12515386 A JP12515386 A JP 12515386A JP S62283124 A JPS62283124 A JP S62283124A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- aromatic
- group
- polyamide resin
- bis
- 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 - Lifetime
Links
- 229920006122 polyamide resin Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 239000004760 aramid Substances 0.000 claims description 15
- 229920003235 aromatic polyamide Polymers 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000006157 aromatic diamine group Chemical group 0.000 claims 1
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 abstract description 10
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- WDAIEUUMGUXKIK-UHFFFAOYSA-N 5-[1,1,1,3,3,3-hexafluoro-2-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]propan-2-yl]-n-trimethylsilyl-2-trimethylsilyloxyaniline Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(C(C=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 WDAIEUUMGUXKIK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920002577 polybenzoxazole Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- UHZFBWOVYRBPAE-UHFFFAOYSA-N 2,3,6-trifluoro-5-propan-2-ylidene-4-(2,3,4-trifluorophenyl)cyclohex-3-ene-1,1-dicarbonyl chloride Chemical compound FC1=C(C(=C(C=C1)C=1C(C(C(C(C=1F)F)(C(=O)Cl)C(=O)Cl)F)=C(C)C)F)F UHZFBWOVYRBPAE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PGJDKGMYQNFEDQ-UHFFFAOYSA-N 3-n-trimethylsilyl-1-n-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]-4-trimethylsilyloxybenzene-1,3-diamine Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(NC=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)=C1 PGJDKGMYQNFEDQ-UHFFFAOYSA-N 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- SJVGFKBLUYAEOK-SFHVURJKSA-N 6-[4-[(3S)-3-(3,5-difluorophenyl)-3,4-dihydropyrazole-2-carbonyl]piperidin-1-yl]pyrimidine-4-carbonitrile Chemical compound FC=1C=C(C=C(C=1)F)[C@@H]1CC=NN1C(=O)C1CCN(CC1)C1=CC(=NC=N1)C#N SJVGFKBLUYAEOK-SFHVURJKSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MWHHJYUHCZWSLS-UHFFFAOYSA-N FC=1C=C(C=CC1C1=C2CNC(C2=C(C=C1)C=1NC(=CN1)C)=O)NC(=O)NC1=C(C=C(C=C1F)F)F Chemical compound FC=1C=C(C=CC1C1=C2CNC(C2=C(C=C1)C=1NC(=CN1)C)=O)NC(=O)NC1=C(C=C(C=C1F)F)F MWHHJYUHCZWSLS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- DTEURMGDDRLGHQ-UHFFFAOYSA-N bis[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]methanone Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(C(=O)C=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)=C1 DTEURMGDDRLGHQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- DSOUSWYEUBCOFS-UHFFFAOYSA-N n-trimethylsilyl-4-[4-(trimethylsilylamino)-3-trimethylsilyloxyphenyl]-2-trimethylsilyloxyaniline Chemical group C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC=C1C1=CC=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=C1 DSOUSWYEUBCOFS-UHFFFAOYSA-N 0.000 description 1
- SGFZGUPEVMQHJJ-UHFFFAOYSA-N n-trimethylsilyl-5-[2-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]propan-2-yl]-2-trimethylsilyloxyaniline Chemical compound C=1C=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC=1C(C)(C)C1=CC=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=C1 SGFZGUPEVMQHJJ-UHFFFAOYSA-N 0.000 description 1
- JKBBCAVZVYJPNA-UHFFFAOYSA-N n-trimethylsilyl-5-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenoxy]-2-trimethylsilyloxyaniline Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(OC=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)=C1 JKBBCAVZVYJPNA-UHFFFAOYSA-N 0.000 description 1
- XRRKVRSXXSBWAJ-UHFFFAOYSA-N n-trimethylsilyl-5-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]sulfanyl-2-trimethylsilyloxyaniline Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(SC=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)=C1 XRRKVRSXXSBWAJ-UHFFFAOYSA-N 0.000 description 1
- ZLKIYYJJEWJVIT-UHFFFAOYSA-N n-trimethylsilyl-5-[3-(trimethylsilylamino)-4-trimethylsilyloxyphenyl]sulfonyl-2-trimethylsilyloxyaniline Chemical compound C1=C(O[Si](C)(C)C)C(N[Si](C)(C)C)=CC(S(=O)(=O)C=2C=C(N[Si](C)(C)C)C(O[Si](C)(C)C)=CC=2)=C1 ZLKIYYJJEWJVIT-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 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
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 229960000368 sulisobenzone Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、芳香族ポリアミド樹脂の新規な製造方法に関
する。一般に芳香族ポリアミド樹脂は、優れた耐熱性、
ｌＩ！ａ械的強度、電気的特性を持つことが知られてい
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing aromatic polyamide resins. In general, aromatic polyamide resins have excellent heat resistance,
lI! It is known to have good mechanical strength and electrical properties.
本発明は特に次の一般式（１）で示される芳香族ポリア
ミド樹脂の製造に関するものであり、一般式
（式中、Ｒは２１西の芳香族基、Ｘは２価の有機基、ｎ
は１〜２００の整数を示す、）
この構造のポリアミド樹脂は、脱水環化反応させること
により、容易に芳香族ポリベンズオキサゾール樹脂を製
造することができる。The present invention particularly relates to the production of an aromatic polyamide resin represented by the following general formula (1), in which R is an aromatic group, X is a divalent organic group, n
represents an integer of 1 to 200.) The polyamide resin having this structure can be easily produced into an aromatic polybenzoxazole resin by subjecting it to a cyclodehydration reaction.
一般に高分子樹脂の性質を決定する上で、分子量の与え
る影響は重要である１重合度が低く、分子量が小さい場
合は、粘性や柔軟性が不充分となり、膜、繊維、成形品
に加工することが困難である。また、加工しても、強度
や耐熱性等に充分な性質が得られない、一方、分子量が
大きすぎる場合は、樹脂の流動性が悪くなり、加工時の
障害となる。In general, the influence of molecular weight is important in determining the properties of polymer resins.If the degree of polymerization is low and the molecular weight is small, the viscosity and flexibility will be insufficient, making it difficult to process into membranes, fibers, and molded products. It is difficult to do so. Furthermore, even when processed, sufficient properties such as strength and heat resistance cannot be obtained. On the other hand, if the molecular weight is too large, the fluidity of the resin deteriorates, which becomes an obstacle during processing.
分子量は、原料の仕入量によって制御される０例えば、
芳香族ポリアミド樹脂の場合は、芳香族ジアミン化合物
と芳香族ジカルボン酸シバライドを有機溶媒中で反応さ
せることにより一般的に製造されるが、これらの反応成
分を等モル量使用とすると、高分子量の芳香族ポリアミ
ド樹脂を製造することができる。しかしながら、このよ
うな分子量の制御は、原料である反応成分の反応性が充
分高い場合にのみ可能であり、反応性が悪い場合には、
分子量の低い反応生成物しか得られない。The molecular weight is controlled by the amount of raw materials purchased. For example,
Aromatic polyamide resins are generally manufactured by reacting an aromatic diamine compound and an aromatic dicarboxylic acid civalide in an organic solvent, but if these reaction components are used in equimolar amounts, high molecular weight Aromatic polyamide resins can be produced. However, such control of molecular weight is only possible when the reactivity of the reaction components as raw materials is sufficiently high; if the reactivity is poor,
Only reaction products with low molecular weights are obtained.
従来、本発明の目的物である芳香族のポリアミド樹脂は
その反応成分であるジアミン化合物の反応性が悠いため
に、高分子量の重合体を１５ることが困難であった９本
発明考らは、充分に高分子量で、優れた性質を発揮する
芳香族ポリアミド樹脂を得るべく鋭意努力した結果、本
発明をなすに至った。Conventionally, it was difficult to prepare a high molecular weight polymer for aromatic polyamide resin, which is the object of the present invention, because the reactivity of the diamine compound, which is a reactive component thereof, was slow. As a result of intensive efforts to obtain an aromatic polyamide resin that has a sufficiently high molecular weight and exhibits excellent properties, the present invention has been completed.
〔問題点を解決するための具体的な手段］すなわち本発
明は、
一般式
（式中、Ｒは２価の芳香族基、Ｘは２価の有機基、ｎは
１〜２００の整数を示す、）
で表される芳香族ポリアミド樹脂を製造するに当り一般
式
（式中、Ｒ１は１価の有機珪素基、Ｒ′は水素、または
１１ｉ！ｌｉの有機珪素基、Ｘは２価の有機基を示す。[Specific means for solving the problem] That is, the present invention is based on the general formula (wherein, R is a divalent aromatic group, X is a divalent organic group, and n is an integer of 1 to 200. , ) In producing the aromatic polyamide resin represented by the general formula (where R1 is a monovalent organosilicon group, R' is hydrogen or an organosilicon group of 11i!li, and X is a divalent organic Indicates the group.
）で表される芳香族ジアミンと
一般式
％式％）
（式中、Ｒは２価の芳香族基、Ｙはハロゲンを示す。）
で表される芳香族ジカルボン酸シバライドとを有機溶媒
中で反応させることを特徴とする、芳香族ポリアミド樹
脂の製造方法である。) and the general formula % formula %) (In the formula, R represents a divalent aromatic group and Y represents a halogen.)
This is a method for producing an aromatic polyamide resin, which is characterized by reacting an aromatic dicarboxylic acid cybaride represented by the following in an organic solvent.
上記一般式（１）で表される芳香族ポリアミド樹脂は、
上記一般式（■）で表される芳香族ジアミンと、上記一
般式（［［Ｉ）で表されるジカルボン酸シバライドとの
反応によって製造される。The aromatic polyamide resin represented by the above general formula (1) is
It is produced by a reaction between an aromatic diamine represented by the above general formula (■) and a dicarboxylic acid cybaride represented by the above general formula ([[I)].
一般式（［１）で表される芳香族ジアミンとしては、式
中Ｘで表される２ １ｉ１の有機基として、単結合、ア
ルキレン基、ハロゲン化アルキレン基、スルホン基、ス
ルフィド基、アミノ基、カルボニル基、エーテル基等が
あげられるが、より具体的に例示すると、ビス（３−ト
リメチルシリル７ミノー・１−トリメチルシロキシフェ
ニル）メタン、】−フェニル−１，１−ビス （３−ト
リメチルアミノ−４−トリメチルシロキシフェニル）エ
タン、２．２−ビス（３−トリメチルシリルアミノ−４
−トリメチルシロキシフェニル）プロパン、２．２−ビ
ス（３−トリメチルシリルアミノ−４−トリメチルシロ
キシフェニル）へキサフルオロプロパン、Ｉ−フェニル
−１，１−ビス（３−トリメチルシリルアミノ−４−ト
リメチルシロキンフェニル）トリフルオロエタン、ｌ−
トリフルオロメチル−１，１−ビス（３−トリメチルシ
リルアミノ−４−トリメチルシロキシ）エタン、（４，
４’−ビス（トリメチルソリルアミノ） −３，３−ビ
ス （トリメチルシロキシ）〕ビフェニル、（３，３−
ビス（トリメチルシリルアミノ） −４，４’−ビス
（トリメチルシロキシ）〕ピフェニル、ビス（３−トリ
メチルシリルアミノ−４−トリメチルシロキンフェニル
）スルホン、ビス（３−トリメチルシリルアミノ−４−
トリメチルシロキシフェニル）スルフィド、ビス（３−
トリメチルシリルアミノ−４−トリメチルシロキシフェ
ニル）エーテル、ビス（３−トリメチルシリルアミノ−
４−トリメチルシロキシフェニル）ケトン、ビス（３−
トリメチルシリルアミノ−４−トリメチルシロキシフェ
ニル）アミン等が有効である。As the aromatic diamine represented by the general formula ([1), the organic group of 2 1i1 represented by Examples include carbonyl group, ether group, etc., but more specific examples include bis(3-trimethylsilyl7mino-1-trimethylsiloxyphenyl)methane, ]-phenyl-1,1-bis(3-trimethylamino-4 -trimethylsiloxyphenyl)ethane, 2,2-bis(3-trimethylsilylamino-4
-trimethylsiloxyphenyl)propane, 2,2-bis(3-trimethylsilylamino-4-trimethylsiloxyphenyl)hexafluoropropane, I-phenyl-1,1-bis(3-trimethylsilylamino-4-trimethylsiloxyphenyl) ) trifluoroethane, l-
Trifluoromethyl-1,1-bis(3-trimethylsilylamino-4-trimethylsiloxy)ethane, (4,
4'-bis(trimethylsorilamino)-3,3-bis(trimethylsiloxy)]biphenyl, (3,3-
Bis(trimethylsilylamino)-4,4'-bis(trimethylsiloxy)]piphenyl, bis(3-trimethylsilylamino-4-trimethylsilyloxyphenyl)sulfone, bis(3-trimethylsilylamino-4-
trimethylsiloxyphenyl) sulfide, bis(3-
Trimethylsilylamino-4-trimethylsiloxyphenyl) ether, bis(3-trimethylsilylamino-
4-trimethylsiloxyphenyl)ketone, bis(3-
Trimethylsilylamino-4-trimethylsiloxyphenyl)amine and the like are effective.
一般式（１■）で表される芳香族ジカルボン酸シバライ
ドとしては、例えばイソフタル酸ジクロリド、テレフタ
ル酸ジクロリド、４．４’−ビフェニルジカルボン酸ジ
クロリド、ビフェニルエーテル４．４１−ジカルボン酸
ジクロリド、ベンゾフェノン−４，４１−ジカルボン酸
ジクロリド、ベンゾスルホン−４，４′−ジカルボン酸
ジクロリド、インプロピリデンビフェニル−４，４１−
ジカルボン酸ジクロリド、ヘキサフルオロイソプロピリ
デンビフェニル−４，４＋−ジカルボン酸ジクロリド等
を例示できる。これらは単独でも、２種類以上を混合し
て用いてもよい。Examples of the aromatic dicarboxylic acid civalide represented by the general formula (1) include isophthalic acid dichloride, terephthalic acid dichloride, 4,4'-biphenyldicarboxylic acid dichloride, biphenyl ether 4,41-dicarboxylic acid dichloride, benzophenone-4 , 41-dicarboxylic acid dichloride, benzosulfone-4,4'-dicarboxylic acid dichloride, inpropylidene biphenyl-4,41-
Examples include dicarboxylic acid dichloride, hexafluoroisopropylidene biphenyl-4,4+-dicarboxylic acid dichloride, and the like. These may be used alone or in combination of two or more.
この方法において、一般式（１）で表されるポリアミド
樹脂の分子量は、一般式（Ｉｔ）で表されるジアミン化
合物と、一般式（［［Ｉ）で表されるジカルボン酸シバ
ライドの仕入量によって制限され、これらの反応成分を
等モル量使用すると高分子量の芳香族ポリアミド樹脂を
製造することができる。In this method, the molecular weight of the polyamide resin represented by the general formula (1) is determined by the amount of the diamine compound represented by the general formula (It) and the dicarboxylic acid civalide represented by the general formula ([[I)]. If these reaction components are used in equimolar amounts, a high molecular weight aromatic polyamide resin can be produced.
一般式（］）で表されるポリアミド樹脂の製造方法は、
有機溶媒中、実質上無水の条件下で上記一般式（■）で
表される芳香族ジアミン化合物と一般式（ＩＩ）で表さ
れるジカルボン酸シバライドとを一１０℃から溶媒の還
ｔ／Ｘ温度で数分から数時間反応させて行われる。The manufacturing method of polyamide resin represented by the general formula (]) is as follows:
The aromatic diamine compound represented by the above general formula (■) and the dicarboxylic acid civalide represented by the general formula (II) are mixed in an organic solvent under substantially anhydrous conditions from -10°C to reflux t/X of the solvent. The reaction is carried out at a high temperature for several minutes to several hours.
この方法に使用できる有＃！Ａ溶媒は、一般に公知の非
水県有１１１ｆｆｉ媒を広範囲に用いることができる。This method can be used! As the solvent A, a wide range of generally known non-aqueous 111ffi media can be used.
具体的には、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、
ピリジン等のアミド系溶媒、ジメチルスルホキシド、テ
トラメチルスルホン等のイオウ系溶媒、ベンゼン、トル
エン、アニソール、ジフェ且ルエーテル、ニトロベンゼ
ン、ベンゾニトリル、クレゾール、フェノール等のベン
ゼン系溶媒、クロロホルム、トリクロルエタン、四塩化
炭素等のハロゲン化炭化水素水素等を例示できるが、こ
れに限定されるものではない。Specifically, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone,
Amide solvents such as pyridine, sulfur solvents such as dimethylsulfoxide and tetramethylsulfone, benzene solvents such as benzene, toluene, anisole, diphenyl ether, nitrobenzene, benzonitrile, cresol, and phenol, chloroform, trichloroethane, and tetrachloride. Examples include halogenated hydrocarbons such as carbon, but are not limited thereto.
本発明により得られる芳香族ポリアミドは、耐熱性に優
れ、その分解温度は４００℃以上と高（、また強度も大
である。さらに本発明で得られる芳香族ポリアミド樹脂
は、多くの有機溶剤に可溶であり、膜、繊維等の成形お
よび塗料材料等として有用である。また、本発明で得ら
れるポリアミドは構造中に水酸基を有しており、脱水環
化反応により容易により耐熱性、強度に優れたポリベン
ズオキサゾール樹脂が得られるものである。The aromatic polyamide obtained by the present invention has excellent heat resistance, its decomposition temperature is as high as 400°C or higher (and its strength is also high. Furthermore, the aromatic polyamide resin obtained by the present invention is resistant to many organic solvents. It is soluble and is useful for forming membranes, fibers, etc. and as coating materials.Also, the polyamide obtained by the present invention has hydroxyl groups in its structure, and can easily be improved in heat resistance and strength through a dehydration cyclization reaction. A polybenzoxazole resin with excellent properties can be obtained.
以下、本発明を実施列によって更に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to examples.
（実施例−１）
容Ｒ５０ｍｆの三つロフラスコに２．２−ビス（３−ト
リメチルシリルアミノ−４−トリメチルシロキシフェニ
ル）へキサフルオロプロパン１．６３８ｇ （２，５ｍ
ｎ＋ｏｌ） 、ジメチルアセトアミド５ｍｌを採り、窒
素ガス雰囲気下で攪拌溶解した。この溶液をドライアイ
ス−アセトン浴で凍結した後、イソフタル酸ジクロリド
０．５０８ｇ （２，５ｍ ｌ ）を添加した。(Example-1) 1.638 g of 2,2-bis(3-trimethylsilylamino-4-trimethylsiloxyphenyl)hexafluoropropane (2.5 m
n+ol), 5 ml of dimethylacetamide was taken and dissolved with stirring under a nitrogen gas atmosphere. After freezing this solution in a dry ice-acetone bath, 0.508 g (2.5 ml) of isophthalic acid dichloride was added.
水冷塔に替えて、５時間ゆっくり攪拌した後、溶液を水
中に投入し、ポリドアミド樹脂の沈°澱をｆ’ｌた。生
成樹脂の固有粘土は０．６４ （０，５ｔＪ ｄＬジメ
チルアセトアミド、３０℃）であった。After slowly stirring for 5 hours using a water cooling tower, the solution was poured into water to remove the precipitate of the polyamide resin. The inherent clay of the resulting resin was 0.64 (0.5 tJ dL dimethylacetamide, 30°C).
赤外線吸収スペクトルおよび元素分析の結果式 の構造であることを確認した。Infrared absorption spectrum and elemental analysis result formula It was confirmed that the structure was
赤外線吸収スペクトル ＋６００Ｃ１１１（Ｎ−
Ｈ）１６５０ｃＩｌｌ （Ｃ＝Ｏ）
元素分析
ＨＮ
計算値（％） ５５．６６ ２．８４ ５．６４実測
値（％） ５５．４４ ２．６８ ５．８８（実施例
−２）
（実施例−１）と同じ方法で、２．２−ビス（３−トリ
メチルシリルアミノ−４−トリメチルシロキンフェニル
）へキサフルオロプロパン１．６３８ｇ （２，５ｍｍ
ｏｌ ）と、テレフタル酸クロリド０．５０８ｇ （２
，５ｍｍｏｌ ）を反応させ、ポリアミド樹脂を得た。Infrared absorption spectrum +600C111 (N-
H) 1650 cIll (C=O) Elemental analysis HN Calculated value (%) 55.66 2.84 5.64 Actual value (%) 55.44 2.68 5.88 (Example-2) (Example-1 ), 1.638 g of 2,2-bis(3-trimethylsilylamino-4-trimethylsiloquinphenyl)hexafluoropropane (2,5 mm
ol ) and 0.508 g of terephthalic acid chloride (2
, 5 mmol) to obtain a polyamide resin.
生成樹脂の固有粘土は、０．６５ （０，５ｇ／ ｄＬ
ジメチルアセトアミド、３０℃）であった。The inherent clay of the produced resin is 0.65 (0.5g/dL
dimethylacetamide, 30°C).
元素分析、赤外線吸収スペクトル分析の結果を第１表に
示した。The results of elemental analysis and infrared absorption spectrum analysis are shown in Table 1.
（以下、実施例３〜８、比較例Ｉの結果も第１表に示し
た。）
この結果より、下式の構造であることを確認した。(Hereinafter, the results of Examples 3 to 8 and Comparative Example I are also shown in Table 1.) From these results, it was confirmed that the structure was as shown in the following formula.
（実施例−３）
（実施例−１）と同じ方法で、２．２−ビス（３−トリ
メチ少シリルアミノー４−トリメチルシロキシフェニル
）ヘキ（サフルオロプロパン１．６３８ＪＩ （２，５
ｍｍｏｌ ）と、イソフタル酸クロリド０．２５４ｇ
（１，２５ｍｍｏｌ） とテレフタル酸クロリド０．２
５４ｇ （１，２５ｍｍｏｌ）を反応させ、ポリアミド
樹脂ヲ得り。(Example-3) In the same manner as in (Example-1), 2,2-bis(3-trimethyolisilylamino-4-trimethylsiloxyphenyl)hex(safluoropropane 1.638JI (2,5
mmol) and 0.254 g of isophthalic acid chloride.
(1.25 mmol) and terephthalic acid chloride 0.2
54g (1.25mmol) was reacted to obtain a polyamide resin.
生成樹脂の固有粘度は０．８６ （０，５ｇ／ ｄＬジ
メチルアセトアミド、３０℃）であった。分析の結果、
次式の構造であった。The intrinsic viscosity of the resulting resin was 0.86 (0.5 g/dL dimethylacetamide, 30° C.). As a result of the analysis,
The structure was as follows.
（実施例−４）
（実施９ｌ−１）と同じ方法で、２．２−ビス（３−ト
リメチルシリルアミノ−４−トリメチルシロキンフェニ
ル）へキサフルオロプロパン１．６３８ｇ （２，５ｗ
＋ｍｏｌ ）と、ビフェニルエーテル−４，４１−ジカ
ルボン酸ジクロリド０．７３７ｇ （２，５＠１Ｉｏｌ
）を反応させ、ポリアミド樹脂を得た。(Example-4) In the same manner as (Example 9l-1), 1.638 g (2,5w
+mol) and 0.737g of biphenyl ether-4,41-dicarboxylic acid dichloride (2,5@1Iol
) was reacted to obtain a polyamide resin.
生成樹脂の固有粘度は０．４７ （０，５ｇ／ｄＬ、ジ
メチルアトアミド、３０℃）であった０分析の結果、次
式の構造であることを確認した。The intrinsic viscosity of the resulting resin was 0.47 (0.5 g/dL, dimethyl atomamide, 30°C). As a result of analysis, it was confirmed that it had the structure of the following formula.
（以下余白）
（実施例−５）
（実施例−１）と同じ方法で、２．２−ビス（３−トリ
メチルシリルアミノ−４−トリメチルシロキシフェニル
）へキサフルオロプロパン１．６３８ｇ （２，５ｍｍ
ｏｌ ） と２．６−サツクレンシカルボン酸ジクロリ
ド０．６３３ｇ （２，５ｍｍｏｌ ）を反応させ、ポ
リアミド樹脂を得た。生成樹脂の固有粘度は０．６０（
０，５ｇ／ｄＬジメチルアセトアミド、３０℃）であっ
た。分析の結果、次式の構造であることを確認した。(Left below) (Example 5) Using the same method as in Example 1, 1.638 g of 2,2-bis(3-trimethylsilylamino-4-trimethylsiloxyphenyl)hexafluoropropane (2.5 mm
ol) and 0.633 g (2.5 mmol) of 2,6-sucrenesicarboxylic acid dichloride were reacted to obtain a polyamide resin. The intrinsic viscosity of the produced resin is 0.60 (
0.5 g/dL dimethylacetamide, 30°C). As a result of the analysis, it was confirmed that the structure was as shown in the following formula.
（実施例−６）
（実施汐１１−１１ と同じ方法で、２．２−ビス（３
−トリメチルンリルγミノー４−トリメチルシロキシフ
ェニル）へキサフルオロプロパン１．６３８ｇ （２，
５ｍｍｏｌ ）と、ヘキサフルオロイソプロピリデンビ
フェニル−４，４−ジカルボン酸ジクロリド１．０７３
ｇ （２，５ｍ＠ｏｌ ）を反応させ、ポリアミド樹脂
をｉｉ４だ、生成樹脂の固有粘度は０．４０ （０，５
ｇ／ ｄＬジメチルアセトアミド、３０℃）であった。(Example-6) (2.2-bis(3
1.638 g (2,
5 mmol) and 1.073 hexafluoroisopropylidene biphenyl-4,4-dicarboxylic acid dichloride.
g (2,5 m@ol) and polyamide resin ii4, the intrinsic viscosity of the resulting resin is 0.40 (0,5
g/dL dimethylacetamide, 30°C).
分析の結果、次式の構造であることを確認した。As a result of the analysis, it was confirmed that the structure was as shown in the following formula.
（実施例−７）
（実施例−１）と回し方法で、２．２−ビス（３−トリ
メチルシリルアミノ−４−トリメチルシロキンフェニル
）プロパン１．３６８ｇ （２，５ｍｍｏ＋ ） と、
イソフタル酸クロリド０．５０８１ｉ （２，５１１
Ｉｍｏｌ ）を反応させ、ポリアミド樹脂を肖な。生成
樹脂の固有粘度は０．５５ （０，５ｇ／ ｄＬジメチ
ルアセトアミド、３０℃）であった。分析の結果、次式
の構造であることを確認した。(Example-7) Using the rotating method as in (Example-1), 1.368 g (2.5 mmo+) of 2,2-bis(3-trimethylsilylamino-4-trimethylsiloquinphenyl)propane,
Isophthalic acid chloride 0.5081i (2,511
Imol) to form a polyamide resin. The intrinsic viscosity of the resulting resin was 0.55 (0.5 g/dL dimethylacetamide, 30° C.). As a result of the analysis, it was confirmed that the structure was as shown in the following formula.
（実施例−８）
（実施例−１）と同じ方法で、４．４′−ビス（トリメ
チルシリルアミノ） −３，３’−ビス（トリメチルシ
ロキシ）ビフェニル１．２６２ｇ （２，５ｍｍｏｌ
）とイソフタル酸クロリド０．５０８ｇ （２，５ｍｍ
ｏｌ ）を反応サセ、ホ＋Ｊ ｙ ミｔ’４Ｈ脂１１り
。(Example-8) Using the same method as in (Example-1), 1.262 g (2.5 mmol) of 4,4'-bis(trimethylsilylamino)-3,3'-bis(trimethylsiloxy)biphenyl
) and isophthalic acid chloride 0.508g (2.5mm
ol ) to the reaction sequence, ho+J y mit'4H fat 11re.
生成樹脂の固有粘度は０．５０ （０，５ｇ／ ｄＬジ
メチルアセトアミド、３０℃）であった０分析の結果、
次式の構造であることをｎｔｇした。As a result of analysis, the intrinsic viscosity of the produced resin was 0.50 (0.5 g/dL dimethylacetamide, 30°C).
ntg that it has the structure of the following formula.
（比較例−１）
（実施例−１）と同じ条件で、２．２−ビス（３−アミ
ノ−４、ヒドロキンフェニル）へキサフルオロプロパン
０．９１５ｇ（２，５ｍｍｏｌ ） とイソフタル酸ク
ロリド０．５０８ｇ （２，５ｍｍｏｌ ）を反応させ
、ポリアミド樹脂を得た。生成物は、（実施例−１）で
製造したポリアミド樹脂と１司じ構造であった。(Comparative Example-1) Under the same conditions as in (Example-1), 0.915 g (2.5 mmol) of 2,2-bis(3-amino-4,hydroquinphenyl)hexafluoropropane and 0.0 g of isophthalic acid chloride .508 g (2.5 mmol) was reacted to obtain a polyamide resin. The product had a one-unit structure with the polyamide resin produced in (Example-1).
生成ポリアミド樹脂の固有粘度は、０．０８ （０，５
ｇ／ ｄＬジメチルアセトアミド、３０℃）であった。The intrinsic viscosity of the produced polyamide resin is 0.08 (0,5
g/dL dimethylacetamide, 30°C).
（以下余白）
第１表
（本発明の効果）
本発明は、一般式（＋）で表される芳香族ポリアミド樹
脂の有利な！！遣方法を提供するものである。この樹脂
は耐熱性、耐候性、機械強度、電気的特性等の諸性質が
良好であり、優れた工業的材料であることが知られてい
るが、従来、高分子量の樹脂を製造することが困難であ
った。これに対し、本発明は、充分に高分子量の当該樹
脂を製造するための有利な方法を提供するものであり、
工業的価値が商い。(The following is a blank space) Table 1 (Effects of the present invention) The present invention has advantages of the aromatic polyamide resin represented by the general formula (+)! ! It provides a method for sending money. This resin has good properties such as heat resistance, weather resistance, mechanical strength, and electrical properties, and is known to be an excellent industrial material. It was difficult. In contrast, the present invention provides an advantageous method for producing such resins of sufficiently high molecular weight,
Industrial value is the trade.
特許出願人 セントラル硝子株式会社代 理 人
弁理士 坂 本 栄 −「−−］： １
−一〜ノPatent applicant Central Glass Co., Ltd. Agent
Patent Attorney Sakae Sakamoto −”−−]: 1 −1～ノ
Claims (1)
１〜２００の整数を示す。） で表される芳香族ポリアミド樹脂を製造するに当り、一
般式 ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾１は１価の有機珪素基、Ｒ＾２は水素また
は１価の有機珪素基、Ｘは２価の有機基を示す。）で表
される芳香族ジアミンと ▲数式、化学式、表等があります▼（III） （式中、Ｒは２価の芳香族基、Ｙはハロゲンを示す。）
で表される芳香族ジカルボン酸ジハライドを有機溶媒中
で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。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R is a divalent aromatic group, X is a divalent organic group, and n is an integer from 1 to 200.) In producing the aromatic polyamide resin represented by the general formula ▲mathematical formula, chemical formula, table, etc.▼(II) (In the formula, R^1 is a monovalent organosilicon group, R^2 is hydrogen or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R is a divalent aromatic diamine) group, Y represents a halogen.)
A method for producing a polyamide resin, which comprises reacting an aromatic dicarboxylic acid dihalide represented by the formula in an organic solvent.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12515386A JPS62283124A (en) | 1986-05-30 | 1986-05-30 | Production of polyamide resin |
| GB08712400A GB2191496A (en) | 1986-05-30 | 1987-05-27 | Method of preparing aromatic polyamides and polybenzoxazoles |
| US07/054,965 US4820793A (en) | 1986-05-30 | 1987-05-28 | Method of preparing aromatic polyamides and polybenzoxazoles |
| DE19873718212 DE3718212A1 (en) | 1986-05-30 | 1987-05-29 | METHOD FOR PRODUCING AROMATIC POLYAMIDES AND POLYBENZOXAZOLES |
| IT20732/87A IT1205115B (en) | 1986-05-30 | 1987-05-29 | METHOD FOR PREPARING AROMATIC POLYAMIDS AND POLYBENZOSSAZOLS |
| FR878707596A FR2599370B1 (en) | 1986-05-30 | 1987-05-29 | PROCESS FOR THE PREPARATION OF AROMATIC POLYAMIDES AND POLYBENZOXAZOLES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12515386A JPS62283124A (en) | 1986-05-30 | 1986-05-30 | Production of polyamide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62283124A true JPS62283124A (en) | 1987-12-09 |
Family
ID=14903184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12515386A Expired - Lifetime JPS62283124A (en) | 1986-05-30 | 1986-05-30 | Production of polyamide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62283124A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021098867A (en) * | 2016-03-30 | 2021-07-01 | 国立大学法人 東京大学 | Novel polymer having aldaric acid as constitutional unit and method for producing the same |
-
1986
- 1986-05-30 JP JP12515386A patent/JPS62283124A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021098867A (en) * | 2016-03-30 | 2021-07-01 | 国立大学法人 東京大学 | Novel polymer having aldaric acid as constitutional unit and method for producing the same |
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| EXPY | Cancellation because of completion of term |