CN100453579C

CN100453579C - Process for preparing soluble polyimide

Info

Publication number: CN100453579C
Application number: CNB2004100537022A
Authority: CN
Inventors: 贺飞峰; 吕珏; 于娜
Original assignee: Shanghai Huayi Group Corp
Current assignee: Shanghai Huayi Group Corp
Priority date: 2004-08-13
Filing date: 2004-08-13
Publication date: 2009-01-21
Anticipated expiration: 2024-08-13
Also published as: CN1587298A

Abstract

Aromatic dianhydride and aromatic diamine according to equimolar ratio react in an N-methyl pyrrolidone/xylene mixed solvent in the presence of isoquinoline or beta-picoline as a catalyst at the temperature of 150DEG C to 180DEG C for 2 to 8 hours and react at the temperature of 180DEG C to 210DEG C for 0.25 to 8 hours, and a glass plate or a metal plate or a plastic film after the xylene is distilled off is directly coated with a polymer solution and respectively heated at the temperatures of 100DEG C, 160DEG C and 250DEG C for one hour to obtain a polyimide film with the number average molecular weight Mn of 50000 to 160000, the weight average molecular weight Mw of 120000 to 280000, the tensile strength of 85 to 120MPa and the tensile rate of 6.9 to 10%.

Description

The preparation method of soluble polyimide

(1) technical field

The present invention relates to the preparation method of soluble polyimide, relate to the preparation method that aromatic dianhydride and aromatic diamine condensation reaction prepare solubility homopolymerization or copolyimide or rather.

(2) background technology

Soluble polyimide is dissolvable in water in the polar aprotic solvent, for its processing and utilization bring great convenience, has expanded its purposes, can be used as moulding compound, coating, tackiness agent etc. with regard to kind.Aromatic diamine by replacements such as alkyl, alkoxyl group, cycloalkyl, aralkyl, can improve its second-order transition temperature and thermostability on its amino nitrogen-atoms ortho position.For this reason, Switzerland Ciba-Geigy company has made extensive work in this respect.The said firm has prepared soluble polyimide with aromatic series dianhydride and aromatic diamine and blend thereof, has obtained good result.Prior art USP4,629,777.December16 1986. at least one ortho position by aromatic series tetracarboxylic acid dianhydride and nitrogen-atoms are changed into equal polyimide and copolyimide by the aromatic diamine that alkyl, alkoxyl group, alkoxyalkyl, cycloalkyl or aralkyl replace.This polyimide dissolves in organic solvent, has high glass-transition temperature and extraordinary thermostability.Because contain the benzophenone tetracarboxylic dianhydride component, so to radiation sensitive, but illumination is crosslinked, is applicable to the production of film protective coating and photography relief image.Concrete use-case comprises electronic component protection, insulation and passivation lacquer, electronic component photomask, textile printing, planar design artwork; printed wiring, printing plate and unicircuit etching agent, X-ray photomask, the structural unit of multilayer circuit dielectric substance and liquid-crystal display.Prior art is by benzophenone tetracarboxylic dianhydride (BTDA) and 4,4 '-diamino-3, and 3 '-dimethyl-5,5 '-diethyl ditan carries out reaction with same mole, and temperature of reaction is 50 ℃.BTDA divides and adds for three times in the reactive system, and mixture cool to room temperature after reaction ends adds triethylamine and aceticanhydride again and carries out chemical imidization, and with water precipitation, filtration, drying, the polyimide feature viscosity that the result makes is 0.70dL/g, Tg282 ℃.This process prepares polyimide with two step method, complicated operating process, long reaction time, and these all are need be improved.

Present inventors once made catalyzer with isoquinoline 99.9, made solvent with meta-cresol/xylene mixture, and allow aromatic series dianhydride and aromatic diamine carry out condensation reaction and prepare polyimide, through ethanol sedimentation, filtration, the dry polyimide powder that gets.The powder dissolution after drying of filming in pimelinketone obtains Kapton.The recyclable utilization of meta-cresol solvent that this method is used, but unavoidable residual meta-cresol in the residue, to environment can pollute and the prior art of front relatively, still to precipitate, separate, it is long that preparation process seems, needs improvement too.

(3) summary of the invention

The present invention is exactly in order to overcome the shortcoming of prior art, provides easy and simple to handle, flow process is short, polymericular weight is high, the better preparation method of tensile property.

The present invention by etc. the aromatic series dianhydride and the aromatic diamine of mol ratio be 1-5 in weight ratio: in 1 N-Methyl pyrrolidone/dimethylbenzene mixed solvent, in charging capacity is in the presence of the 0.1-2% weight part β-picoline or isoquinoline 99.9 catalyzer of total charging capacity, in 150-180 ℃ of condensation reaction 2-8 hour, 180-210 ℃ was reacted 0.25-8 hour, directly polymkeric substance-N-Methyl pyrrolidone solution coat on carrier, here said carrier can be a sheet glass, metal sheet, plastics film etc., in 100 ℃, 160 ℃, 250 ℃ are respectively heated after 1 hour and obtain Kapton, control polyimide number-average molecular weight Mn is 50000-160000, weight-average molecular weight is Mw120000-280000, film stretching intensity is 85-120MPa, elongation 6.9-10%.

Aromatic series dianhydride of the present invention is a pyromellitic acid anhydride, 3,3 ', 4, and 4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4, any one in 4 '-diphenyl ether tetraformic dianhydride, the dihydroxyphenyl propane dianhydride.

Used aromatic diamine is 4,4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditan.

β-picoline or isoquinoline 99.9 catalyst consumption are the 0.2-1% weight ratio of total charging capacity.

Setting-up point and time are 160-175 ℃/3-6 hour preferably, 185-200 ℃/0.25-4 hour.

Operation such as the present invention relatively saves chemical imidization, water or ethanol sedimentation with prior art, separate, after the polymers soln that reaction obtains can directly be coated with, carry out the heat drying film forming again, the polyimide number-average molecular weight is between 50,000-160,000, weight-average molecular weight is between 120,000-280,000, the film stretching intensity of producing is 85-120MPa, elongation 6.8-10%.

(4) embodiment

In order to implement the present invention better, especially exemplified by example it is described, but is not limitation of the present invention.

Example 1

Be equipped with agitator, thermometer, nitrogen inlet, add 4 in the 500ml there-necked flask of water trap and condenser, 4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditan 16.92g (0.06 mole), N-Methyl pyrrolidone (NMP) 240g and dimethylbenzene 100ml, logical nitrogen, stirring and dissolving, add pyromellitic acid anhydride (PMDA) 13.08g (0.06 mole) and catalyzer isoquinoline 99.9 0.18g then, lasting stirring is warming up to more than 165 ℃, begins to distillate water in 170 ℃, sustained reaction 5 hours, about the about 4ml of water outlet, after heat temperature raising steams dimethylbenzene 100ml then, be warming up to 195 ℃ of reactions 4 hours, obtain the burgundy viscous solution, directly this polymers soln is coated on the sheet glass, through 100 ℃, 160 ℃, 200 ℃, 250 ℃ were respectively heated 1 hour, and obtained Kapton, its tensile strength is 105MPa, elongation is 8.1%, Mn125216, Mw237714.

Example 2

Divided by 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA) 17.64 (0.06 mole) replaces pyromellitic acid anhydride, the isoquinoline 99.9 catalyzer was 0.42g, and N-Methyl pyrrolidone adds 86g, in 170 ℃ of reactions 4 hours, 200 ℃ were reacted outside 0.25 hour, other and example 1 are just the same, Tensile Strength of Polyimide Film 123MPa as a result, elongation 10%, Mn92518, Mw213245.

Example 3

Divided by 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride (BTDA) 19.32g (0.06 mole) replaces pyromellitic acid anhydride, the isoquinoline 99.9 catalyzer was 0.52g, and the amount of N-Methyl pyrrolidone is 430g, in 175 ℃ of reactions 3 hours, 190 ℃ were reacted outside 4 hours, other and example 1 are just the same, and Tensile Strength of Polyimide Film is 120MPa as a result, elongation 7.6%, Mn65819, Mw145852.

Example 4

Divided by 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride (0DPA) 18.60g (0.06 mole) replaces pyromellitic acid anhydride, the isoquinoline 99.9 catalyzer is 0.72g, in 160 ℃ of reactions 6 hours, outside 200 ℃ of reactions 2 hours, other and example 1 were just the same, Tensile Strength of Polyimide Film is 115MPa as a result, elongation 8.2%, Mn66600, Mw162963.

Example 5

Replace pyromellitic acid anhydride divided by dihydroxyphenyl propane dianhydride (BPADA) 17.64g (0.06 mole), in 175 ℃ of reactions 3 hours, 185 ℃ were reacted outside 4 hours, other and example 1 are just the same, and Tensile Strength of Polyimide Film is 85MPa as a result, elongation 9.7%, Mn72652, Mw138430.

Example 6-10

Except that catalyzer β-picoline 0.18g replaced isoquinoline 99.9, other was the same with example 1.The result is as follows:

Example number	Example 6	Example 7	Example 8	Example 9	Example 10
Example number	Example 6	Example 7	Example 8	Example 9	Example 10	Aromatic dianhydride	PMDA	BPDA	BTDA	ODPA	BPADA
Mn	116921	1159518	105856	54004	87473	Aromatic dianhydride	PMDA	BPDA	BTDA	ODPA	BPADA
Mn	116921	1159518	105856	54004	87473	Mw	234689	272634	242662	128198	145514
Tensile strength, MPa	100	109	111	106	93.1	Mw	234689	272634	242662	128198	145514
Tensile strength, MPa	100	109	111	106	93.1	Extensibility, %	9.0	6.9	8.8	8.6	9.0

Claims

1, the preparation method of soluble polyimide, it is characterized in that aromatic dianhydride and aromatic diamine are 1-5 in weight ratio: in 1 N-Methyl pyrrolidone/dimethylbenzene mixed solvent, in charging capacity is in the presence of 0.1～2% weight part β-picoline or isoquinoline 99.9 catalyzer of total charging capacity, in 150-180 ℃ of condensation reaction 2-8 hour, 180-210 ℃ was reacted 0.25-8 hour, after steaming dimethylbenzene, directly polymkeric substance-N-Methyl pyrrolidone solution coat on carrier, in 100 ℃, 160 ℃, 250 ℃ are respectively heated after 1 hour and obtain Kapton, and control polyimide number-average molecular weight Mn is 50000-160000, and weight-average molecular weight is Mw120000-280000.

2, according to the preparation method of the soluble polyimide of claim 1, it is characterized in that described aromatic dianhydride is a pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4, any one in 4 '-diphenyl ether tetraformic dianhydride, the dihydroxyphenyl propane dianhydride.

3, according to the preparation method of the soluble polyimide of claim 1, it is characterized in that described aromatic diamine is 4,4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditan.

4, according to the preparation method of the soluble polyimide of claim 1, it is characterized in that described β-picoline or isoquinoline 99.9 charging capacity are the 0.2-1% weight ratio of total charging capacity.

5,, it is characterized in that described condensation reaction is 160-175 ℃/3-6 hour, 185-200 ℃/0.5-4 hour according to the preparation method of the soluble polyimide of claim 1.

6, according to the preparation method of the soluble polyimide of claim 1, the condensation reaction that it is characterized in that described aromatic dianhydride and aromatic diamine such as is at the reaction of mol ratio.