CN1302046C - Preparation method of soluble polyimide - Google Patents
Preparation method of soluble polyimide Download PDFInfo
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- CN1302046C CN1302046C CNB2004100537018A CN200410053701A CN1302046C CN 1302046 C CN1302046 C CN 1302046C CN B2004100537018 A CNB2004100537018 A CN B2004100537018A CN 200410053701 A CN200410053701 A CN 200410053701A CN 1302046 C CN1302046 C CN 1302046C
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Abstract
The present invention relates to a preparation method of soluble polyimide, which comprises: 4, 4'-diamino-3, 3'-dimethyl-5, 5'-diethyldiphenylmethane and aromatic dianhydride, such as pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride and bisphenol A dianhydride, react in an m-cresol/xylene mixed solvent in the presence of isoquinoline as a catalyst at the temperature of 150 to 180DEG C for 2 to 8 hours and react at the temperature of 180 to 200DEG C for 0.25 to 8 hours to carry out an equimolar reaction to obtain the soluble polyimide with 15000 to 110000 of Mn and 30000 to 250000 of Mw. The linear expansion coefficient of the soluble polyimide is from 19 to 60 ppm, the tensile strength is from 91 to 133MPa, and the extension rate is from 5 to 10.8%.
Description
Technical field
The present invention relates to the preparation method of soluble polyimide, relate to the polymer repeat unit structure or rather and be
The preparation method of soluble polyimide, wherein Ar can be
Among them any or their mixture,
R is
Background technology
Polyimide is the thermotolerance macromolecular material with excellent comprehensive performance.Since E.I.Du Pont Company's exploitation industrialization of the sixties U.S., it is applied in every field.Especially use more at Aeronautics and Astronautics, microelectronics and military industry field.Because polyimide generally is insoluble to organic solvent, so, process with the presoma polyamic acid of favorable solubility usually, and then carry out the imidization processing acquisition polyimide of dehydration closed-loop.But polyamic acid is comparatively responsive to moisture, can not prolonged storage.So that on some degree, limited its application.Up to the present, the approach that solves the polyimide solubility has only three kinds.One adopts fluorochemical monomer to synthesize fluorinated polyimide; Its two, adopt monomer synthesis of polyimides with the bulky group in resistance position, destroy the conjugacy of main chain; Its three, adopt synthetic semi-aromatic of alicyclic monomer or non-aromatic polyimide.First method is because the fluorochemical monomer price is expensive, so limited application surface, the third method kind is few, and price is also expensive, and thermotolerance decreases.Second kind of way monomer is easy to get, moderate cost, and product properties can accomplish the end in view, so, be used in a large number.Prior art Te Kaiben 3-252378, on November 11st, 1991 is open, adopts 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride and 4,4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditane, 4,4 '-diaminodiphenyl oxide reacts synthesizing polyamides acid in N-Methyl pyrrolidone, logarithm viscosity is 2.5dL/g, and curtain coating is carried out hot imidization and obtained the polyimide glued membrane on film.The anti-tin-welding of this glued membrane is good, and outward appearance is no abnormal, and adhesive power is 1.20-1.28kg/25mm.The bonding condition of this glued membrane and Copper Foil is pressurization 5-10kg/cm
2, 320 ℃ * 10 minutes.The purpose product of prior art is a glued membrane, is 1.20-1.28kg/25mm (471-502N/m) so adhesive power data of glued membrane only are provided, so that other physical and mechanical properties of cast film do not provide, and the application to it can be restricted like this.
Summary of the invention
The present invention adopts various aromatic series dianhydrides, for example: pyromellitic acid anhydride, diphenyl ether tetraformic dianhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, dihydroxyphenyl propane dianhydride are respectively with 4,4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditane is made catalyzer with isoquinoline 99.9 in the mixed solvent of dimethylbenzene and meta-cresol, by dimethylbenzene band water, condensation reaction and one step of dehydration imidization are finished reaction, obtain the imido powder of high-molecular-weight poly with ethanol sedimentation again.This polyimide powder dissolves in the like methylene dichloride of common organic solvent, chloroform, dimethyl formamide, pimelinketone, tetrahydrofuran (THF), the N-Methyl pyrrolidone, shelf lives is long, convenient transportation, solidification value low (250 ℃), good film-forming property, the film toughness height, linear expansivity is lower, can be made into film, moulding compound, tackiness agent, coating and fiber etc.
Its polymer repeat unit structure of soluble polyimide that makes with the present invention is
Wherein Ar is
In the composition colony any one, R is
Next step condensation reaction of effect at catalyzer and dewatering agent in organic solvent is prepared from this soluble polyimide by aromatic dianhydride and aromatic diamine.
Aromatic dianhydride of the present invention can be chosen any one kind of them from pyromellitic acid anhydride, diphenyl ether tetraformic dianhydride, benzophenone tetracarboxylic acid dianhydride, bibenzene tetracarboxylic dianhydride and dihydroxyphenyl propane dianhydride, prepares solvable polyimide.
The used aromatic diamine of the present invention is 4,4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditane.
Used organic solvent is the mixture of meta-cresol and dimethylbenzene, and their weight ratio is 1-5: 1, and weight ratio is 2-4 preferably: 1.
Used catalyzer is an isoquinoline 99.9, and consumption is the 0.2-2% weight percent of total charging capacity.
The used dewatering agent of the present invention means dimethylbenzene.
Described condensation reaction parameter is 150-180 ℃ of reaction 2-8 hour, and 180-210 ℃ of reaction 0.25-8 hour, reaction parameter was 160-170 ℃ of reaction 3-6 hour preferably, 185-200 ℃ of reaction 0.5-4 hour.
The soluble polyimide that makes with the present invention has number-average molecular weight Mn15000-110000, weight-average molecular weight Mw30000-250000, saturated water absorption 0.9-2.8%, film stretching intensity 91.2-133MPa, elongation 5-10.8%, linear expansivity 19.1-60ppm (50-150 ℃), 25-70ppm (150-250 ℃).
Embodiment
Especially exemplified by example it is described in order to implement the present invention better, but is not limitation of the present invention.
Embodiment 1
Be equipped with agitator, thermometer, nitrogen inlet, add 4 in the there-necked flask of the 500ml of water trap and condenser, 4 '-diamino-3,3 '-dimethyl-5,5 '-diethyl ditane 16.92g (0.06 mole), meta-cresol 240g and dimethylbenzene 100ml, logical nitrogen, the stirring and dissolving diamines, then add pyromellitic acid anhydride (PMDA) 13.08g (0.06 mole) and catalyzer isoquinoline 99.9 0.18g, be warming up to 165 ℃ while stirring, temperature is kept 175 ℃ of reactions 3 hours, distillate the about 3ml of water, continue to steam dimethylbenzene 95ml, be warming up to 195 ℃ of reactions 3 hours, obtain the burgundy viscous solution, it is poured in the ethanol, under high-speed stirring, be settled out polyimide, filtration with washing with alcohol after, obtain polyimide powder through 100 ℃ of vacuum-dryings.Use the gel permeation chromatograph determining molecular weight, number of results average molecular weight (Mn) is 17872, and weight-average molecular weight (Mw) is 55868.Making solid content with pimelinketone dissolving is 12% solution, and curtain coating heats in baking oven on sheet glass.Branch respectively removed in 80 ℃, 120 ℃, 160 ℃, 200 ℃, 250 ℃ and desolvates in 1 hour, obtain the yellow polyimide film, it has tensile strength 97.2MPa, elongation 7.3%, second-order transition temperature Tg is greater than 350 ℃, linear expansivity 19.1ppm (50-150 ℃), 25.5ppm (150-250 ℃), saturated water absorption 2.8%.
Embodiment 2
Remove with bibenzene tetracarboxylic dianhydride 17.63g (0.06 mole) and replace pyromellitic acid anhydride, mixed solvent is meta-cresol 172g and dimethylbenzene 100ml, and catalyzer isoquinoline 99.9 0.07g was in 160 ℃ of reactions 6 hours, outside 184 ℃ of reactions 4 hours, other is just the same with example 1.The result is the number-average molecular weight Mn53803 of polyimide, weight-average molecular weight Mw151866, Tg281 ℃, saturated water absorption 1.7%, tensile strength 115MPa, elongation 10%, linear expansivity 36.1ppm (50-150 ℃), 42.2ppm (150-250 ℃).
Embodiment 3
Remove with benzophenone tetracarboxylic dianhydride 19.32g (0.06 mole) replacement pyromellitic acid anhydride, catalyzer isoquinoline 99.9 0.25g, meta-cresol 344g and dimethylbenzene 100ml, in 165 ℃ of reactions 4 hours, 200 ℃ were reacted outside 0.5 hour, and other is the same with example 1.The result is the number-average molecular weight Mn105856 of polyimide, weight-average molecular weight Mw242662, tensile strength 111MPa, elongation 8.8%, Tg350 ℃, saturated water absorption 1.86%, linear expansivity 34.1ppm (50-150 ℃), 55.1ppm (150-250 ℃).
Embodiment 4
Remove with phenyl ether tetracarboxylic dianhydride 18.6g (0.06 mole) replacement pyromellitic acid anhydride, catalyzer isoquinoline 99.9 0.35g, meta-cresol 430g and dimethylbenzene 100ml, in 180 ℃ of reactions 2 hours, 210 ℃ were reacted outside 0.25 hour, and other is the same with example 1.The result is the number-average molecular weight Mn31341 of polyimide, weight-average molecular weight Mw73679, saturated water absorption 1.5%, tensile strength 113MPa, elongation 7%.
Embodiment 5
Remove with dihydroxyphenyl propane dianhydride 31.2g (0.06 mole) replacement pyromellitic acid anhydride, catalyzer isoquinoline 99.9 0.7g, mixed solvent are meta-cresol 86g and dimethylbenzene 100ml, and in 150 ℃ of reactions 8 hours, outside 180 ℃ of reactions 8 hours, other was the same with example 1.The polyimide that the result obtains has number-average molecular weight Mn49713, weight-average molecular weight Mw87060, Tg238 ℃, saturated water absorption 0.9%, tensile strength 88.4MPa, elongation 5.5%, linear expansivity 23ppm (50-150 ℃), 45ppm (150-250 ℃).
Claims (8)
1, the polymer repeat unit structure is
The preparation method of soluble polyimide, be characterised in that:
Ar be by
Choose any one kind of them in the colony that forms,
R is
This kind soluble polyimide is by the aromatic dianhydride of correspondence and aromatic diamine, and in organic solvent, under the effect of catalyzer and dewatering agent, a step condensation reaction prepares;
Described aromatic diamine is 4,4 '-diamino-3.3 '-dimethyl-5,5 '-the diethyl ditan.
2, the preparation method characteristic according to the soluble polyimide of claim 1 is that described aromatic dianhydride is to choose any one kind of them in pyromellitic acid dianhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride or the dihydroxyphenyl propane dianhydride.
3, the preparation method characteristic according to the soluble polyimide of claim 1 is that described organic solvent is the mixture of meta-cresol and dimethylbenzene, and their weight ratio is 1-5: 1.
4, the preparation method characteristic of soluble polyimide according to claim 4 is that the weight ratio of described organic solvent meta-cresol and dimethylbenzene is 2-4: 1.
5, the preparation method characteristic according to the soluble polyimide of claim 1 is that described catalyzer is an isoquinoline 99.9, and consumption is the 0.2-2 weight % of total charging capacity.
6, the preparation method characteristic of soluble polyimide according to claim 1 is that described dewatering agent is a dimethylbenzene.
7, the preparation method according to the soluble polyimide of claim 1 is characterized in that described condensation reaction is 150-180 ℃ of reaction 2-8 hour, 180-210 ℃ of reaction 0.25-8 hour.
8, the preparation method of soluble polyimide according to Claim 8 is characterized in that described condensation reaction is 160-170 ℃ of reaction 3-6 hour, 185-200 ℃ of reaction 0.5-4 hour.
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| CNB2004100537018A CN1302046C (en) | 2004-08-13 | 2004-08-13 | Preparation method of soluble polyimide |
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| CNB2004100537018A CN1302046C (en) | 2004-08-13 | 2004-08-13 | Preparation method of soluble polyimide |
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| CN101177484B (en) * | 2006-11-08 | 2010-06-09 | 同济大学 | Bisphenol A-type polyimide material and method for making same |
| CN102604093B (en) * | 2012-03-26 | 2013-09-25 | 长春高琦聚酰亚胺材料有限公司 | Preparation method of polyimide |
| CN114716675B (en) * | 2022-03-04 | 2023-10-27 | 江苏环峰电工材料有限公司 | Adjustable water-soluble battery binder and preparation method thereof |
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| US6713597B2 (en) * | 2002-03-19 | 2004-03-30 | General Electric Company | Preparation of polyimide polymers |
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| US6713597B2 (en) * | 2002-03-19 | 2004-03-30 | General Electric Company | Preparation of polyimide polymers |
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