CN1006394B - Aromatic polyimide composition - Google Patents
Aromatic polyimide compositionInfo
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- CN1006394B CN1006394B CN 85103494 CN85103494A CN1006394B CN 1006394 B CN1006394 B CN 1006394B CN 85103494 CN85103494 CN 85103494 CN 85103494 A CN85103494 A CN 85103494A CN 1006394 B CN1006394 B CN 1006394B
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- aromatic
- aromatic polyimide
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Abstract
The present invention relates to an aromatic polyimide composition which can be used for producing formed products, such as thin films, or used as varnish, spraying paint or adhesive agents. The aromatic polyimide resin containing high molecular weight is a polycondensing product, namely an imine reaction product of an aromatic tetracarboxylic acid component and an aromatic diamine component, wherein the aromatic tetracarboxylic acid contains more than 50 g molecule percentage of 3, 4, 4', 4'-biphenyl tetracarboxylic acid or acid anhydride, salt or ester thereof; the aromatic diamine contains more than 50 g molecule percentage of 4, 4'-diamino-diphenyl ether. The product is dissolved in the following mixed solution which contains phenol or resorcine as a first solvent component accounting for more than 10% (by weight), and phenol or cresol as a second solvent component matched with the first solvent component.
Description
The relevant aromatic polyimide composition of the present invention.In more detail, the invention relates to the preparation of high-molecular weight aromatic polyimide in aromatic polyimide composition.This polymkeric substance is to contain acid constituents by one, mainly be 3,4,3 ', 4 '-biphenyltetracarboxyacid acid, with one contain amine component, mainly be 4,4 '-the diamines yl diphenyl ether, be dissolved in and be prepared from the mixed solvent of naphthols or Resorcinol class, it has good long term storage stability, and can be used to produce moulded products, and these goods have excellent mechanical property and electrical property.
As everyone knows, the production of aromatic polyimide divided for two steps carried out.In this process, aromatic tetracarboxylic acid's component and aromatic diamine component under lower temperature, are for example carried out polycondensation under 30 ℃ or lower temperature in organic polar solvent.Obtained dissolved polyamic acid in organic polar solvent.Then, polyamic acid changes into corresponding aroma adoption imide.
Recently, learn that aromatic polyimide can adopt single stage method to carry out.This selects special fragrance family's tetracarboxylic acid component and special fragrance family diamine components to carry out single stage method polycondensation and imidization in polar organic solvent and under the higher temperature with regard to needing.For example: US Patent specification 3,666, No. 709 and 4,247, No. 443 and Japan special permission bulletin 46-17145 number, 47-23191 number, the preparation process that aromatic polyimide solution is all narrated in 47-26878 number and 48-26958 number, in this process, in the aromatic acid component as 3 of main sour composition, 4,3 ', 4 '-benzophenone tetracarboxylic acid dicarboxylic anhydride with as the reaction of the mol such as aromatic diamines component of aromatic amine component, in phenolic solvent, at high temperature, carry out polycondensation and imidization with single stage method.
Similarly, US Patent specification, 3,988, No. 303 and day disclosure special permission bulletin have also all been reported for 51-81899 number with single stage method and have been produced aromatic polyimide solution.In this process, in the acid constituents as 3,4,3 of main sour composition ', 4 '-benzophenone tetracarboxylic dianhydride or 1,4,5,8-naphthalene tetracarboxylic acid dianhydride and aromatic amine component are carried out polycondensation and imidization with single stage method.
In addition, Japan's special permission bulletin is mentioned a kind of polyimide resin composition 47-37706 number, and said composition adopts the tetracarboxylic acid component of lipid acid.
Above-mentioned prior art, polyimide compositions or solution, when they make various moulded products, for example during membrane product, the mechanical property of its resulting product makes us very dissatisfied.The polyimide goods that make with the polyimide solution of usually producing with two step method relatively, membrane product for example, then its tensile strength is very poor, is 10～15kg/mm
2, the two step method product is to use the tetracarboxylic acid component, pyromellitic dianhydride for example, and with amine component, for example 4 carries out that polycondensation and imidization obtain.
Day disclosure special permission 50-113 has narrated by 3,4 for No. 597,3 ', 4 '-biphenyltetracarboxyacid acid or 2,3,3 ', 4 '-method of biphenyltetracarboxyacid acid production solubility aromatic polyimide.This aromatic polyimide dissolves in the phenolic solvent, for example between-cresols, or xylenol.The lacquer that can be used for being coated with electrical wiring or cable is provided.Yet the mechanical property of the coated film goods of gained can not be satisfactory.
US Patent specification 4,290, the solution of narrating polyimide compositions No. 936 can be used for producing the moulded products of polyimide, for example, and the polyimide membrane product, it has the good mechanical performance.This type aromatic polyimide composition solution, can contain 80 moles of % or more 3 by one, 4,3 ', 4 '-the aromatic acid component and of biphenyltetracarboxyacid acid contains 70 moles of % or more 4,4 '-the aromatic amine component of diamines yl diphenyl ether, in the solvent that contains the halogenated phenol compound, temperature is to carry out polycondensation under 100 ℃ to 300 ℃ and imidization is produced.According to US Patent specification 4,290, the example 2 in No. 936 is the polyimide membrane product that 2.38 polyimide solution is produced with logarithmic viscosity number, has good tensile strength, and 21.4 kilograms/square millimeter, ultimate elongation is 98%.Yet, from containing halogenated phenol compound, 4-chlorophenol for example, the polyimide solution that makes in the solvent of 4-bromophenol or 4-fluorophenol is produced polyimide film goods and other moulded products, even temperature is raise, solvent in membrane product or other goods is removed, so also can be contained a spot of halogenide.In some occasion, use aromatic polyimide, for example in electron device, during as high-precision circuit card, halogen compounds is strict forbidden, because they can cause the decline of electron device electrical property.Can be used as between the also having of solvent-nitrophenols and pyrocatechol, can dissolve 5% high molecular aromatic polyimide resin by weight, yet, when between adopting-during nitrophenols, the cost of resulting composition becomes higher, because-nitrophenols price height, and from the gained moulded products, remove and compartment-nitrophenols also is difficult with distillation method.Equally, when adopting pyrocatechol, it is dissatisfied that the mechanical property of the moulded products of gained and electrical property also make us, because pyrocatechol decomposes easily.
Industry member needs aromatic polyimide composition strongly, wishes that it can be completely free of above mentioned those shortcomings.
The purpose of this invention is to provide the composition of the aromatic polyimide that can be used for producing moulded products, these goods not only have the good mechanical performance, but also have good electrical properties.
Another object of the present invention provides the aromatic polyimide composition that has high stability in standing storage.
Another object of the present invention provides and can be used as varnish, sprays paint and the aromatic polyimide composition of tackiness agent.
Above-described purpose can be reached by aromatic polyimide composition of the present invention.It comprises following two components: (1) high-molecular weight aromatic polyimide resin, it is from as 3 of the main sour composition of aromatic tetracarboxylic acid's component, 4,3 ', 4 '-the selected at least a compound that goes out in biphenyltetracarboxyacid acid and acid anhydrides, salt and the ester, carry out with 4,4 ' diaminodiphenyl oxide that polycondensation-imidization makes as the main amine component of aromatic diamine component.(2) mixed solvent, basically contain first solvent that accounts for by weight more than 10%, it can be selected at least a compound from aphthols and Resorcinol class, also contain second solvent composition of arranging in pairs or groups mutually with it, can select at least aly from phenol and cresols class, the two forms mixed solvent.Aromatic polyimide can be dissolved in this solvent.
In aromatic polyimide composition, an aromatic polyimide resin is dissolved in the mixed solvent.
Aromatic polyimide resin is the product that is obtained through polycondensation-imidization by aromatic tetracarboxylic acid's component and aromatic diamine component.
An acid is arranged as main component in this aromatic tetracarboxylic acid's component.Can be from 3,4,3 ', 4 '-select in biphenyltetracarboxyacid acid and acid anhydrides, salt and the ester at least a.And in aromatic tetracarboxylic acid's component 3,4,3 ', 4 '-biphenyltetracarboxyacid acid or its functional derivatives, their consumption, reasonable is to get 50～100 mol %, is more preferably to get 80～100 mol %.In aromatic tetracarboxylic acid's component, except containing main sour composition, can also contain the auxiliary acid composition as essentially consist, can be from pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 3,4,3 ', 4 '-benzophenone tetracarboxylic acid, 2,2 '-two (3,4-two carboxyphenyls) select in propane, two (3,4-two carboxyphenyls) sulfone, two (3,4-two carboxyphenyls) ether and acid anhydrides, salt and the ester at least a, its consumption can be got 50 mol % or below the 50 mol %, preferably gets 20 mol % or below the 20 mol %.
This aromatic diamine component can be used 4.That is to say, in the aromatic diamine component content of 4 reasonable be to get 40～100 mol %, be more preferably and get 50～100 mol %, that best is 70～100 mol %.
In the aromatic diamine component,, the auxiliary amine as essentially consist can also be arranged, and can from following compounds, select at least a except comprising the 4.Example 4,4 '-diamines-3,3 '-dimethyl diphenyl, 4,4 '-diamino-diphenyl thioether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-3,3 '-dimethyl diphenyl ether, 1,4-benzo diamines, 1,3-benzo diamines, 4,4 '-chrysoidine, 4,4 '-diamino diphenyl sulfone and 4,4 '-diaminobenzophenone.General consumption is 40 mol % or below the 40 mol %.Reasonable consumption is 50 mol % or below the 50 mol %.Best consumption is 30 mol % or below the 30 mol %.
Producing an example in the aromatic polyimide resin process, is to use aromatic tetracarboxylic acid's component with the polycondensation of aromatic diamine component, and gained polycondensation product (polyamic acid) imines changes into corresponding polyimide then.
And another example in producing the aromatic polyimide resin process, it is polycondensation with aromatic tetracarboxylic acid's component and aromatic diamine component, then, the imidization of polycondensation product is under suitable high-temperature, for example from 90 ℃ to 200 ℃, in solvent, carry out single stage method that Here it is.The used preferably used same type of mixed solvent of mixed solvent in the reaction of single stage method with synthesis of polyimides of the present invention.
In the reaction process of single stage method, can produce water, it generates as the by product that reacts.When polycondensation and imidization, water can be dispersed in the reaction soln, can steam with azeotropic water is removed from gained solution with partial solvent.
Can be used for this aromatic polyimide resin of the present invention, have higher molecular weight, its corresponding logarithmic viscosity number is 1-2, and this viscosity is to be in/100 milliliters the 4-chlorinated phenol solution of 0.5 gram in concentration, is to record under 50 ℃ of conditions in temperature.
Can be used for this mixed solvent of the present invention, basic composition is (1) and account for first solvent composition more than 10% by weight, preferably from 10% to 90%, be more preferably from 40% to 80%, the first solvent composition can from naphthols and Resorcinol, select in a kind of (2) essentially consist with the collocation of first solvent be second kind of solvent composition, can from phenol, cresols, select a kind of, naphthols comprises naphthyl alcohol, 2-Naphthol, cresols comprises neighbour-cresols ,-cresols and p-Cresol.
With this special mixed solvent of the present invention, the effect of aromatic polyimide resin of dissolving this family macromolecule amount is best, and the concentration of gained solution is the highest.The gained liquid composite is very useful, and it can produce the moulded products with excellent mechanical property and electrical property.
The preparation process of aromatic polyimide composition is that aromatic polyimide resin powder and mixed solvent are mixed and be dissolved in this solvent, and its dissolving service temperature is at 90 ℃ to 200 ℃.In addition, aromatic tetracarboxylic acid's component and aromatic diamine component, be basically with etc. gram molecular weight be dissolved in the mixed solvent with the used same-type of institute of the present invention synthetic aromatic polyimide.Reaction soln under agitation and temperature be to carry out polycondensation and imidization under 90 ℃ to 200 ℃.
In resulting aromatic polyimide composition, the best concentration of polyimide resin is from 2% to 20% by weight, is more preferably from 5% to 15%.Equally, the rotary viscosity of aromatic polyimide composition, preferably from 1 to 200,000 pool is more preferably from 1 to 500 pool.
This aromatic polyimide composition through storing for a long time, still has very high stability.
Therefore, even reach under 100 ℃ in temperature, after aromatic polyimide composition had been stored 15 hours, the rotary viscosity of aromatic polyimide composition still was consistent with original level.
Aromatic polyimide composition can be used to produce moulded products or coating.In this composition, dissolved resin is the resin of complete imidization basically, so, in moulded products or coat operations, do not have water and generate.Usually, this aromatic polyimide synthetics has extremely excellent shaping characteristic (molding or coating), the smooth surface of gained moulded products or coating.
This aromatic polyimide composition, available coating method is transformed into moulded products, and for example film or thin plate also can be used in the coating electrically conductive material, for example electric wire or cable as the coating lacquer.Also can make coating, or make tackiness agent.
The present invention's aromatic polyimide composition needing can be used for being coated with one deck at heating container internal surface and outside surface on the high heat-proof heating container, and heat-resisting like this efficient is just high especially.
In this aromatic polyimide composition of the present invention, make high-molecular weight certain aromatic polyimide resin, mainly be to adopt 3,4,3 ', 4 '-biphenyltetracarboxyacid acid does to contain acid constituents and adopts 4,4 ' diaminodiphenyl oxide to do to contain the amine component reaction and make.Moulded products that makes like this or coating have extremely excellent mechanical property (tensile strength).Simultaneously, in aromatic polyimide composition of the present invention, use special mixed solvent, wherein do not have halogenated compound, nitro-compound and neighbour-oxybenzene compound.Moulded products that this composition makes or coating have satisfied electrical property.Removing and reclaiming of while mixed solvent very easily carry out, and the energy that is consumed is also low.
The present invention will further utilize special example to lay down a definition, yet this is representational, and can not limit the scope of the invention.
Embodiment 1:
At capacity is in the round shape polymerization reactor of 14 liters, add 3 of 540 grams, 4,3 ', 4 ' biphenyltetracarboxyacid acid dicarboxylic anhydride, (hereinafter being referred to as S-BPDA), and with 4 of 360 grams, 4 '-diaminodiphenyl oxide, the N-N-methyl-2-2-pyrrolidone N-of (hereinafter being referred to as DADE) and 6.6 liters is mixed with it together.The mixture of gained at room temperature (is about 25 ℃) and stirred 6 hours, make 3,4,3 ', 4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride and 4 carry out polycondensation.The solution of gained polycondensation product approximately contains 12% polyamic acid by weight, and the rotary viscosity of this solution is approximately 6000 centipoises.The logarithmic viscosity number of the polyamic acid of gained is 2.8.
Agitator, thermometer being housed and having in the there-necked flask of reflux condensing tube of water container, add 2 liters polyamic acid solution, drip 100 milliliters triethylamine subsequently.Reaction mixture heats gradually, and in about 3 hours, temperature of reaction is elevated to 200 ℃ from 140 ℃.At this moment just generated water, and from reactive system, it has been removed.The yellow mercury oxide of reaction mixture is exactly an aromatic polyimide resin.Precipitate crystallization in pelletized form, it is separated from reaction mixture, use methanol wash then, wash with acetone again with filtering method, dry down at 100 ℃ at last.The logarithmic viscosity number of resulting aromatic polyimide resin is 1.18, and the imidization degree is more than 95%, and it is coalesced together by the particulate crystallization forms, and particulate crystalline size is approximately 2 microns.
The preparation of solution is that 15.0 polyimide resins that restrain are dissolved in the mixed solvents of 85.0 grams, and mixed solvent is Resorcinol and phenol, and its weight ratio is 50: 50.Mixture in oil bath and temperature be 110 ℃ time heating 1 hour with dissolving.
15% aromatic polyimide resin is by weight arranged in the gained aromatic polyimide solution, and the rotary viscosity of this solution is 100 pools.
Aromatic polyimide solution is coated on the sheet glass of a level, the coat-thickness that obtains is 0.018 gram per centimeter
2The heating 1 hour when 170 ℃ of temperature of the thin layer of the aromatic polyimide solution of gained, baking is 1 hour in the time of 220 ℃, dries by the fire when final temp reaches 300 ℃ 1 hour again, blows air simultaneously to evaporate mixed solvent.The thickness of the resin film of the aromatic polyimide of gained is 25 microns, and is orange.According to ASTMD882-64T this film is carried out test for tensile strength when 25 ℃ of the temperature, the result is that the tensile strength of thin slice is 21.5 kilograms/millimeter
2, ultimate elongation is 85%.
Embodiment 2:
In capacity is 300 milliliters flask, add 3,4,3 of 10.8 grams ', 4 '-4 and the 82 gram Resorcinols and the 82 phenol blended mixed solvents that restrain of biphenyl carboxylic acids dicarboxylic anhydride, 7.2 grams.Flask is put into the oil bath heating with dissolving.Reaction mixture is heated to temperature to be 170 ℃ and to maintain 170 ℃, the viscosity that stirs reaction mixture at this moment increases with the prolongation of churning time, just in reaction mixture, the molecular weight of aromatic polyimide resin increases with the prolongation in reaction times.
In the weight ratio of Resorcinol and phenol is 50: 50 mixed solvent, by weight, contain 11% polyimide resin, the rotary viscosity of its reaction mixture, 170 ℃ stir 5 hours after, its value is 100 pools (at 100 ℃).And in the time of 170 ℃, stir after 15 hours, then its value is 250 pools (at 100 ℃).That is to say, the rotary viscosity of aromatic polyimide solution, prolongation in time, the value of its increase is little.
Embodiment 3:
Press among the embodiment 2 operation equally, mixed solvent is with the Resorcinols and 60 phenol that restrain of 60 grams.At this moment approximately contain 15%(in the reaction mixture by weight) the gained polyimide resin.The rotary viscosity of such reaction mixture solution stirred 5 hours at 170 ℃, and its value is 1000 pools (at 100 ℃).Stirred 15 hours at 170 ℃, its value is 8000 pools (at 100 ℃).That is to say that the viscosity of polyimide solution or the molecular weight of polyimide resin be with the prolongation of churning time, its viscosity number increases little, and the chlorinated phenol solution of polyimide is with the prolongation in reaction times, and its rotary viscosity then increases widely.
That is to say that polyimide solution of the present invention has demonstrated extremely excellent thermostability and package stability.
At 170 ℃ of solution that contain 15% polyimide resin by weight that stir 15 hours, can be used to prepare thickness and be 25 microns thin slice.Operation is undertaken by example 1 the same manner.
The thin slice of gained, its tensile strength is 20.5 kilograms/millimeter in the time of about 25 ℃
2, its ultimate elongation is 82%.
Embodiment 4:
By the same operation of narration in the example 2, just replace the Resorcinol of 82 grams with the naphthyl alcohol of 82 grams.
Reaction mixture contains 11%(by weight) polyimide, its mixture is 25 pools (at 100 ℃) at 170 ℃ of rotary viscosities that stirred 5 hours.Stir and then be increased to 100 pools (at 100 ℃) in 15 hours.
Embodiment 5:
Carrying out by narration in the example 3 operated equally, just replaces the Resorcinol of 60 grams with the naphthyl alcohol of 60 grams.
Contain 15% polyimide by weight in the reaction mixture, after 5 hours, its value increases to 100 pools (at 100 ℃) to the rotary viscosity of mixture 170 ℃ of stirrings, stirs and then increases to 9000 pools (at 100 ℃) after 15 hours.
With rotary viscosity is that 9000 polyimide solutions of mooring (at 100 ℃) are coated on the sheet glass of level, and with 300 ℃ air ovens bakings 1 hour, the thickness of the film of Huo Deing was 15 microns at last, and is dark brown, and its tensile strength is 19.2 kilograms/millimeter
2, ultimate elongation is 83%, the Young's modulus of tension is 298 kilograms/millimeter
2
Embodiment 6:
The composition of reaction mixture is: 3,4,3 of 6.62 grams ', 4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride, the pyromellitic dianhydride (hereinafter being referred to as PMDA) of 0.55 gram, 4 and a kind of mixed solvent of 50 grams.Mixed solvent is to be mixed by the Resorcinol of 55 grams and 55 phenol that restrain.The reaction mixture heating, and in the time of 170 ℃, stirred 5 hours.
Homogeneous polyimide solution, the 10%(that contains polyimide resin are by weight).Its rotary viscosity is 120 pools (at 100 ℃).
Embodiment 7:
Reaction mixture is made up of following: 3,4,3 of 7.35 grams ', 4 '-the biphenyltetracarboxyacid acid dicarboxylic anhydride, the 4 of 4.50 grams, 4,4 of 5.00 grams '-diaminodiphenyl-methane and mixed solvent.And mixed solvent is the phenol blended by 56 gram Resorcinols and 56 grams.Reactant heated 5 hours in the oil bath of 170 ℃ of temperature.Contain 10%(by weight in the homogeneous phase polyimide solution) polyimide resin, the rotary viscosity of gained solution is 80 pools (at 100 ℃).
Embodiment 8:
Undertaken by the same operation that example 2 is narrated, with between-cresols replaces phenol.Reaction mixture contains 11%(by weight) polyimide, the rotary viscosity of this solution, 170 ℃ stir 5 hours after, its value is 150 pools (at 100 ℃), stirs after 15 hours, its value is 330 to moor (at 100 ℃).
Gained polyimide solution with 330 pool rotary viscosities is coated on the sheet glass, and with air oven baking 1 hour, drying temperature was 100 ℃.The thickness of gained film is 20 microns, is orange, and its tensile strength is 23.0 kilograms/millimeter
2, ultimate elongation is 88%.
Embodiment 9:
Undertaken by the same operation that example 4 is narrated, between just using-cresols replacement phenol.
Reaction mixture contains 11%(by weight) resulting polyimide resin, the rotary viscosity of reaction mixture, 170 ℃ stir 5 hours after, its value increases to 30 pools (at 100 ℃).Stir after 15 hours, its value increases to 120 pools (at 100 ℃).
With rotary viscosity is the polyimide solution of 120 pools, and the same quadrat method of being narrated by embodiment 8 becomes film.
The gained film, its thickness is 23 microns, is dark brown, tensile strength is 19.5 kilograms/millimeter
2And ultimate elongation is 83%.
Embodiment 10:
The coating varnish that the same polyimide solution of being narrated by embodiment 2 is made is coated in diameter and is on 1 millimeter the annealed copper wire, is heated to 100 ℃ of temperature, keeps 30 minutes, keeps 30 minutes under 200 ℃ of temperature again.Formed a coating on the copper cash, its thickness is 50 microns.
Resulting insulated copper wire, breakdown voltage are 13 kilovolts, and be below load 700 grams, wear-resisting more than 100 times.The softening temperature that is heated is 500 ℃.Temperature has excellent stability at 120 ℃ to styrene monomer.
Embodiment 11:
Undertaken by the same operation that embodiment 10 is narrated, just the polyimide solution of being narrated with embodiment 4.
The insulated copper wire of gained, breakdown voltage are 13 kilovolts, and be below 700 gram loads, wear-resisting more than 100 times.The softening temperature that is heated is more than 500 ℃, and the p-poly-phenyl vinyl monomer has fabulous stability.
Claims (8)
1, aromatic polyimide composition, comprising:
(1) high molecular aromatic polyimide resin, it is by aromatic tetracarboxylic acid's component and the aromatic diamine component product through polycondensation-imidization gained, aromatic tetracarboxylic acid as main acid constituents is at least a from 3,4,3 ', 4 '-compound selected in biphenyltetracarboxyacid acid and acid anhydrides, salt and the ester, aromatic diamines is a 4; With
(2) mixed solvent, substantially comprise: account for 10% or more first kind of solvent by weight, its component is at least a compound of selecting from naphthols or Resorcinol, also comprise second kind of solvent with the collocation of first solvent, its component be at least a from phenol or cresols class selected compound, this aromatic polyimide resin is dissolved in this mixed solvent.
2, aromatic polyimide composition according to claim 1, wherein, the logarithmic viscosity number of aromatic polyimide resin is 1 to 2, is to measure in/100 milliliters the 4-chlorinated phenol solution of 0.5 gram in concentration, measuring temperature is 50 ℃.
3, aromatic polyimide composition according to claim 1, wherein, the consumption of main sour composition is 50 to 100 mol % in aromatic tetracarboxylic acid's component.
4, aromatic polyimide composition according to claim 1, wherein, aromatic tetracarboxylic acid's component also contains the auxiliary acid composition except containing main sour composition, and it is at least a compound of selecting from following substantially, pyromellitic acid, 2,3.6。7-naphthalene tetracarboxylic acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 3,4,3 ', 4 '-benzophenone tetracarboxylic acid, 2,2 '-two (3,4-two carboxyphenyls) propane, two (3,4-two carboxyphenyls) sulfone, two (3,4-two carboxyphenyls) ether and acid anhydrides, salt and ester, its consumption are 50 mol % or less than 50 mol %.
5, aromatic polyimide composition according to claim 1, wherein, the consumption of the 4 in the aromatic diamine component is 40 to 100 mol %.
6, aromatic polyimide composition according to claim 1, wherein, the aromatic diamine component remove contain 4,4 '-diamino hexichol phenylate outside, also contain the auxiliary amine composition, it is at least a compound of selecting from following, 4,4 '-diamines-3,3 '-dimethyl diphenyl, 4,4 '-diamino-phenylbenzene-thioether, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-3,3 '-dimethyl diphenyl ether, 1, the 4-phenylenediamine, 1, the 3-phenylenediamine, 4,4 '-chrysoidine, 4,4 '-diamino diphenyl sulfone and 4,4 '-diamino-benzophenone, its consumption is 60 mol % or less than 60 mol %.
7, aromatic polyimide composition according to claim 1, wherein, the meltage of aromatic polyimide in this mixed solvent is 2% to 20% by weight.
8, contain the varnish that right requires 1 described aromatic polyimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103494 CN1006394B (en) | 1984-03-21 | 1985-05-18 | Aromatic polyimide composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59052204A JPS60197759A (en) | 1984-03-21 | 1984-03-21 | Polyimide resin composition |
| CN 85103494 CN1006394B (en) | 1984-03-21 | 1985-05-18 | Aromatic polyimide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103494A CN85103494A (en) | 1986-11-12 |
| CN1006394B true CN1006394B (en) | 1990-01-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103494 Expired CN1006394B (en) | 1984-03-21 | 1985-05-18 | Aromatic polyimide composition |
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| CN (1) | CN1006394B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035113C (en) * | 1992-06-20 | 1997-06-11 | 中国科学院长春应用化学研究所 | Preparation method of thermoplastic polyimide composite material |
| US7267883B2 (en) | 2002-09-25 | 2007-09-11 | Kaneka Corporation | Polyimide film and laminate having metal layer and same |
| CN100469417C (en) * | 2005-03-15 | 2009-03-18 | 大连欧科膜技术工程有限公司 | System for recovering hydrogen from air of methanol synthesis processing by membrane method |
| CN106866964A (en) * | 2015-12-14 | 2017-06-20 | 清华大学 | A kind of polyimide foam and preparation method thereof |
| KR102529151B1 (en) * | 2016-01-27 | 2023-05-08 | 삼성전자주식회사 | Composition for preparing article including polyimide or poly(amide-imide) copolymer, article obtained therefrom, and display device including same |
| KR101959807B1 (en) * | 2018-08-22 | 2019-03-20 | 에스케이씨코오롱피아이 주식회사 | Polyimide Varnish for Coating Conductor Comprising Aromatic Carboxylic Acid and Method for Preparing the Same |
-
1985
- 1985-05-18 CN CN 85103494 patent/CN1006394B/en not_active Expired
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| Publication number | Publication date |
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| CN85103494A (en) | 1986-11-12 |
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