CN103724623A - Method for preparing soluble meltable copolymerized polyimide molding plastic - Google Patents
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Abstract
The invention discloses a method for preparing soluble meltable copolymerized polyimide molding plastic. The method comprises the following steps: preparing polyamide acid from 2,3,3',4'-diphenyl ether pyromellitic dianhydride(a-ODPA), 4,4'-diaminodiphenyl ether(4,4'-ODA) and 1,4-p-phenylenediamine(1,4-PDA) in a ternary polymerization manner together with a mixture of aromatic bianhydride and aromatic diamine through equal molar ratio reaction at room temperature, subsequently adding acetic anhydride, triethylamine and xylene to perform chemical imidization, subsequently filtering, washing in acetone, filtering, drying, screening through a sieve of 100 meshes so as to obtain a copolymerized polyimide powder material, and subsequently performing thermal treatment for 2-3 hours at 220-280 DEG C so as to completely imidize. The prepared copolymerized polyimide powder material has the logarithmic viscosity number of 40ml/g to 110ml/g, the 10wt% loss temperature is 577 DEG C, the retention rate of the tensile strength, the compression strength and the bending strength of a plastic component at 220 DEG C is not greater than 3-5% of that of a homopolymer without 1,4-PDA, and the thermal weight loss temperature and Tg are both increased by 11-12 DEG C.
Description
One. technical field
The present invention relates to a kind of preparation method of solvable meltability copolyimide, relate to or rather 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride reacts with 4，4′-diaminodipohenyl ether and Ursol D the method for preparing copolyimide.
Two. background technology
Polyimide is with high temperature resistant, low temperature resistant, resistance to solvent, the radiation resistance of its excellence, outstanding mechanical strength and dielectric properties etc. are subject to people's great attention, have been widely used in many high-technology fields such as space flight and aviation, automotive industry, microelectronics, flat pannel display.From E.I.Du Pont Company's exploitation at the beginning of the sixties
since film, there is the history of 50 years nearly.This polyimide with pyromellitic acid anhydride (PMDA) and phenyl ether diamines (4,4 '-ODA) linear polymerization gained has excellent performance, but moulding is very difficult.Therefore, machine-shaping difficulty and manufacturing cost height are two critical bottlenecks of its fast development of restriction always.The thermoplastic polyimide of research and development melt-processable is to improve polyimide material processing characteristics, reduce one of main method of manufacturing cost, is also one of polyimide domain expert target of seek assiduously.
By 3,3 ', 4,4 '-diphenyl ether tetraformic dianhydride (ODPA) and 4,4 '-amino-diphenylethers (4,4 '-ODA) polymerization in dimethylacetamide solvent, changes into powder through imines and makes ANALYSIS OF MOLDABLE POLYIMIDES molding powder (s type polydiphenyl ether tetramethyl imide), and its polymer repeat unit structure is as follows:
This thermoplastics in last century the seventies by SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS, succeeded in developing, with trade(brand)name
yS-20 sells so far.These plastics have good mechanics, electrical property, radiation hardness, high-low temperature resistant and wear resisting property, can be-259～220 ℃ of uses.Now as high and low temperature seal washer, valve, piston ring, self-oiling bearing and electrical accessorie etc.But there is the problem of difficult forming in this s type polydiphenyl ether tetramethyl imide, generally need to be 380 ℃ of compression moldings.Recently, from the angle of energy-saving and emission-reduction and raising shaping efficiency, be necessary 380 ℃ of its mold temperatures to reduce greatly, and expectation can injection moulding or extrusion moulding.
Since entering 21 century, Ube company (Ube) and U.S. NASA have dropped into large quantity research to the polyimide PI of isomery biphenyl dianhydride (a-BPDA) simultaneously. find that this polymkeric substance has than the higher glass transition temperature Tg in 4,4 '-position and better processing characteristics.The isomer (2 that China Changchun applied chemistry study Suo Dingmengxian research group takes the lead in to diphenyl ether tetraformic dianhydride (s-ODPA), 3,3 ', 4 '-ODPA) carry out preliminary study (Q.Li with the polyimide of phenyl ether diamines (4,4 '-ODA) etc., X.Fang, Z.Wang, L.Gao, M.Ding, J.Polymer Science, Part A:Polymer Chemistry, Vol.41,3249, (2003)), this 2,3,3 ', 4 '-ODPA/4, the polyimide structures of 4 '-ODA polymerization is as follows:
The Japan horizontal Tian Linan (Yokota of research group of ISAS, Proceeding of Aircraft Symposium, Vol.41, No.3, 602-606 (2003)) and (the 54th International SAMPE Symposium of the Kathy C.Chuang research group of NASA Glenn Research Center, May 18-21, Baltimore, MD (2009)) etc. people is with 2, 3, 3 ', 4 '-diphenyl ether tetraformic dianhydride replaces 3, 3 ', 4, the low molecule performed polymer of the synthetic polydiphenyl ether tetramethyl imide of 4 '-diphenyl ether tetraformic dianhydride or its phenylacetylene benzoic anhydride end-blocking, polyimide resin for RTM moulding.The primary structure of this oligopolymer is:
In addition, horizontal professor Tian Linan also made 2,3,3 ', the polyamides of 4 '-diphenyl ether tetraformic dianhydride and 4，4′-diaminodipohenyl ether is sub-
Amine film, this film has good space environment stability, utilizes its thermal welding performance, the mould material of making solar sail on probation.For the purpose of comparison, the polyimide of this structure is called to a type polydiphenyl ether tetramethyl imide, 3,3 ', 4,4 ' polyimide prepared by-diphenyl ether tetraformic dianhydride is called s type polydiphenyl ether tetramethyl imide.
SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS discloses 2,3,3 ', preparation method's (seeing CN201110417304.4) of the polyimide molding powder of 4 '-diphenyl ether tetraformic dianhydride and 4，4′-diaminodipohenyl ether and moulding compound (YS-20A) thereof.It has good thermotolerance and processing characteristics.In high and new technology field, aerospace field especially, the material higher to thermotolerance has demand.In order further to improve the thermotolerance of moulding compound, keep again its good processibility.A kind of copolyimide moulding compound of novel solvable meltability has been succeeded in developing.The general composition that increases rigid chain segment in polymer segment, can improve high molecular glass transition temperature Tg effectively, but the increase of rigidity composition can make high molecular solvability and thermoplasticity reduce, thereby affects processing characteristics.Here adopt rigidity monomer Ursol D and 2,3,3 ', the combination of 4 '-diphenyl ether tetraformic dianhydride, has solved well thermotolerance and has improved and do not affect solvability and thermoplastic balance.The copolyimide of this novel meltability is by 2,3,3 ', the copolyimide that 4 '-diphenyl ether tetraformic dianhydride and 4，4′-diaminodipohenyl ether and Ursol D copolymerization obtain.By regulating the ratio of Ursol D in diamines, can obtain the copolyimide of different glass transition temperature (Tg).Its Tg can be from 280 ℃～320 ℃.It still keeps good processing characteristics simultaneously.Can shape by hot compacting or other thermoplasticity methods of becoming second nature.
Three. summary of the invention
The preparation method who the object of this invention is to provide a kind of solvable meltability copolyimide, its polymer repeat unit structure formula is as follows.This preparation method comprises following concrete steps:
Step 1, polyamic acid solution preparation: 2,3,3 of employing equimolar ratio ', 4 '-diphenyl ether tetraformic dianhydride and diamines (diaminodiphenyl oxide and blend of p phenylene diamine) are in N,N-DIMETHYLACETAMIDE (DMAc) solution, and room temperature reaction is prepared from for 3～5 hours;
Step 2, chemical imidization: above-mentioned gained copolyamide acid solution is by 100 weight parts, to this copolyamide acid solution, add dewatering agent 40～160 weight parts, tertiary amines organic alkali catalyst 5～50 weight parts and the appropriate nonpolar aromatic hydrocarbons of polyimide precipitation agent, violent stirring 0.5～2 hour, completes imidization; Then, filter the copolyimide powder of separating out, with washing with acetone, filtration, be dried and obtain passing through the copolyimide powder of 100 mesh standard sieves, through after 220 ℃ to 280 ℃ thermal treatment, further improve imidization degree, just obtained and can carry out the molding powder that forming process is used.The logarithmic viscosity number of this copolyimide is at 40ml/g～110ml/g.
Step 3, compression molding processing plastic exemplar: moulded plastics product, mold pressing parameter is 280～350 ℃ of mould temperature, forming pressure 15～70MPa, the molded heat insulation time determines with product thickness, is generally 3～30min.
Moulded parts performance is:
Glass transition temperature Tg: 289 ℃～294 ℃
Weightless 5 % by weight temperature: 540 ℃～551 ℃
Weightless 10 % by weight temperature: 577 ℃～588 ℃
Tensile strength: 23 ℃, 114～120MPa tensile modulus: 23 ℃, 3.00～3.26GPa
220℃，46.4～50.3MPa 220℃，/
Flexural strength: 23 ℃, 151～156MPa modulus in flexure: 23 ℃, 2.90～3.09GPa
220℃，73.9～78.8MPa 220℃，2.06～2.13GPa
Compressive strength: 23 ℃, 156～161MPa modulus of compression: 23 ℃, 2.35～2.40GPa
220℃，63.0～65.4MPa 220℃，1.40～1.42GPa
Shock strength (non-notch): 23 ℃, 152～154J/m.
In the preparation method of solvable meltability copolyimide, aromatic diamine is 4，4′-diaminodipohenyl ether and Ursol D.Ursol D is the 10mol%～90mol% of the amount of the mixture of 4，4′-diaminodipohenyl ether and Ursol D, preferably 20mol%～60mol%.
The preparation method of above-mentioned solvable meltability copolyimide, wherein, any one of described dewatering agent selection aceticanhydride, propionic anhydride or the mixture of the two.
The preparation method of above-mentioned solvable meltability copolyimide, wherein, described catalyzer is selected pyridine, 3, more than any one in 5-lutidine, N-methylmorpholine, 3-picoline, 4-picoline, Trimethylamine 99, triethylamine and isoquinoline 99.9.
The preparation method of above-mentioned solvable meltability copolyimide, wherein, described nonpolar aromatic hydrocarbons, selects in toluene, dimethylbenzene the mixture of any one or the two.
The preparation method of above-mentioned solvable meltability copolyimide, wherein, the consumption of described nonpolar aromatic solvent is with the weighing scale of dimethylacetamide solution in step 1, and its weight percentage is 10～50%.
(a-ODPA/4,4 '-ODA/1,4-PDA) copolyimide molding powder of the solvable meltability of preparing according to the present invention is dissolvable in water in dimethyl formamide or ethanamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) and gamma-butyrolactone.
This preparation method simple process, reaction conditions is gentle, and easy to operate and safe, reaction yield is high, is applicable to industrialized production, and the molding powder of gained is careful evenly, is easy to moulding.And the copolyimide moulding compound that the method processing obtains has than existing a type polyesteramide model plastic, glass transition temperature Tg is high, and the mechanical property conservation rate of 220 ℃ of high temperature is higher, and processing characteristics is suitable, and it will have a good application prospect.
Feature of the present invention is remarkable, adopt terpolymer to prepare solvable fusible copolyimide, with 1mol 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride is basis, add 0.2～0.6mol Ursol D and 0.8～0.4mol 4,4 '-diaminodiphenyl oxide, had both remained on the solvability in organic solvent, can improve thermal characteristics and physical and mechanical properties again.With the exemplar comparison that does not add Ursol D, Tg improves 12 ℃, and in air, the temperature of weightless 10 % by weight improves 11 ℃.Tensile strength, compressive strength and flexural strength all improve 3～5% in the conservation rate measured value of 220 ℃.
The present invention adopts solvent precipitation in chemical imidization process, is conducive to separate out copolyimide powder, is convenient to filtering separation.
The copolyimide of preparing according to the present invention is expected to realize injection moulding and extrusion moulding.Copolyimide solution energy curtain coating becomes film, will be widely used in raising new technical field.
Four, embodiment
In order to implement better the present invention, spy illustrates it, but is not limitation of the present invention.
Embodiment 1
To being equipped with mechanical stirrer, thermometer, in the 5000ml four-hole round-bottomed flask of nitrogen gangway, contain into 160g(0.8mol) 4, 4 '-diaminodiphenyl oxide, 21.6g(0.2mol) Ursol D and 2200ml N,N-DIMETHYLACETAMIDE, stir after dissolving completely, add again 310g(1mol) 2, 3, 3 ', 4 '-diphenyl ether tetraformic dianhydride, in room temperature reaction, after 4 hours, obtain polyamic acid solution, add aceticanhydride 1050g, triethylamine 260g and dimethylbenzene 210g, continue reaction and complete imidization at 1.0 o'clock, the polyimide powder that filtration is separated out, then, with 1000ml acetone, wash three times, filter, at 50～80 ℃, dry 1～2 hour, then 220 ℃～280 ℃ thermal treatments 2～5 hours, the yield that obtains copolyimide is 92%, logarithmic viscosity number is 75ml/g.This polyimide is moulded plastics exemplar under 350 ℃/30MPa, and the performance index of plastics exemplar are as shown in following table-1:
Second-order transition temperature (Tg), 289 ℃
Thermogravimetric analysis 5% loss temperature in air, 540 ℃
10% loss temperature, 578 ℃
Table-1: the mechanical property of embodiment 1 gained copolyimide
| Intensity under room temperature | Intensity at 220 ℃ | 220 ℃ of property retention rates | |
| Tensile strength, MPa | 114 | 46.3 | 40.6% |
| Tensile modulus, GPa | 3.0 | —— | —— |
| Compressive strength, MPa | 156 | 65.4 | 41.9% |
| Modulus of compression, GPa | 2.35 | 1.40 | 60% |
| Flexural strength, MPa | 151 | 73.9 | 48.9% |
| Modulus in flexure, GPa | 2.9 | 2.06 | 71% |
| Unnotched impact strength, J/m | 1729 | —— | —— |
| Notched Izod impact strength, J/m | 152 |
Embodiment 2
To being equipped with in the 5000ml four-hole round-bottomed flask of mechanical stirrer, thermometer, nitrogen gangway, contain into 100g(0.5mol) 4,4 '-diaminodiphenyl oxide, 54g(0.5mol) Ursol D and 2200ml N,N-DIMETHYLACETAMIDE, stir after dissolving completely, add again 310g(1mol) 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride, in room temperature reaction, after 4 hours, obtain polyamic acid solution, after this step is continuous identical with embodiment 1.The yield of molding powder is 88.3%, and logarithmic viscosity number is 61.5ml/g, and second-order transition temperature (Tg) is 303 ℃, and 5% and 10% weight reduces temperature and is respectively 551 ℃ and 577 ℃ (in Table-2).
Table-2: the mechanical property of embodiment 2 gained copolyimides
| Intensity under room temperature | Intensity at 220 ℃ | 220 ℃ of property retention rates | |
| Tensile strength, MPa | 119 | 50.2 | 42.2% |
| Tensile modulus, GPa | 3.22 | —— | —— |
| Compressive strength, MPa | 165 | 67.6 | 41% |
| Modulus of compression, GPa | 2.47 | 1.44 | 58.3% |
| Flexural strength, MPa | 134 | 83.2 | 62.1% |
| Modulus in flexure, GPa | 2.65 | 2.07 | 78.1% |
| Unnotched impact strength, J/m | 1070 | —— | —— |
| Notched Izod impact strength, J/m | 153 |
Embodiment 3
To being equipped with in the 5000ml four-hole round-bottomed flask of mechanical stirrer, thermometer, nitrogen gangway, contain into 130g(0.65mol) 4,4 '-diaminodiphenyl oxide, 37.8g(0.35mol) Ursol D and 2200ml N,N-DIMETHYLACETAMIDE, stir after dissolving completely, add again 310g(1mol) 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride, in room temperature reaction, after 4 hours, obtain polyamic acid solution, after this step is continuous identical with embodiment 1.The yield of molding powder is 88.6%, and logarithmic viscosity number is 67.5ml/g, and glass transition temperature Tg is 294 ℃, and 5% and 10% weight reduces temperature and is respectively 541 ℃ and 581 ℃ (in Table-3).
Table-3: the mechanical property of embodiment 3 gained copolyimides
| Intensity under room temperature | Intensity at 220 ℃ | 220 ℃ of property retention rates | |
| Tensile strength, MPa | 120 | 43.7 | 36.4% |
| Tensile modulus, GPa | 3.26 | —— | —— |
| Compressive strength, MPa | 161 | 63 | 39.2% |
| Modulus of compression, GPa | 2.4 | 1.4 | 59% |
| Flexural strength, MPa | 156 | 78.8 | 50.6% |
| Modulus in flexure, GPa | 3.09 | 2.13 | 68.9% |
| Unnotched impact strength, J/m | 3393 | —— | —— |
| Notched Izod impact strength, J/m | 154 |
Embodiment 4
To being equipped with in the 5000ml four-hole round-bottomed flask of mechanical stirrer, thermometer, nitrogen gangway, contain into 180g(0.9mol) 4,4 '-diaminodiphenyl oxide, 10.8g(0.1mol) Ursol D and 2200ml N,N-DIMETHYLACETAMIDE, stir after dissolving completely, add again 310g(1mol) 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride, in room temperature reaction, after 4 hours, obtain polyamic acid solution, after this step is continuous identical with embodiment 1.The yield of molding powder is 97.4%, and logarithmic viscosity number is 105ml/g, and glass transition temperature Tg is 285 ℃, and 5% and 10% weight reduces temperature and is respectively 540 ℃ and 578 ℃.
Embodiment 5
To being equipped with in the 5000ml four-hole round-bottomed flask of mechanical stirrer, thermometer, nitrogen gangway, contain into 60g(0.3mol) 4,4 '-diaminodiphenyl oxide, 75.6g(0.7mol) Ursol D and 2200ml N,N-DIMETHYLACETAMIDE, stir after dissolving completely, add again 310g(1mol) 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride, in room temperature reaction, after 4 hours, obtain polyamic acid solution, after this step is continuous identical with embodiment 1.The yield of molding powder is 85%, and logarithmic viscosity number is 51.6ml/g, and glass transition temperature Tg is 311 ℃, and 5% and 10% weight reduces temperature and is respectively 544 ℃ and 588 ℃.
Comparative example 1
To being equipped with mechanical stirrer, thermometer, in the 5000ml four-hole round-bottomed flask of nitrogen gangway, contain into 310g(1mol) 2, 3, 3 ', 4 '-diphenyl ether tetraformic dianhydride, 200g4, 4 '-diaminodiphenyl oxide and 2200ml N,N-DIMETHYLACETAMIDE, in room temperature reaction, after 4 hours, obtain polyamic acid solution, add aceticanhydride 1050g, triethylamine 260g and toluene 210g, continue reaction and complete imidization at 1.0 o'clock, the polyimide powder that filtration is separated out, then, with 1000ml acetone, wash three times, filter, at 50～80 ℃, dry 1～2 hour, then 220 ℃～280 ℃ thermal treatments 2～5 hours, obtain a type polyimide 426.6g, yield 90%, this polyimide is moulded plastics exemplar under 310 ℃/30MPa, the performance index of plastics exemplar are as shown in table-4:
Second-order transition temperature (Tg), 277 ℃,
Thermogravimetric analysis 5% loss temperature in air, 551 ℃, 10% loss temperature, 567 ℃.
Table-4: the mechanical property of comparative example 1 gained a type copolyimide
| Intensity under room temperature | Intensity at 220 ℃ | 220 ℃ of property retention rates | |
| Tensile strength, MPa | 119 | 44 | 37.0% |
| Tensile modulus, GPa | 2.96 | —— | —— |
| Compressive strength, MPa | 160 | 60.4 | 37.8% |
| Modulus of compression, GPa | 1.39 | 1.06 | 76.3% |
| Flexural strength, MPa | 168 | 73.7 | 43.9% |
| Modulus in flexure, GPa | 3.22 | 2.08 | 64.6% |
| Unnotched impact strength, J/m | 250 | —— | —— |
| Notched Izod impact strength, J/m | 94 | —— | —— |
Claims (8)
1. a preparation method for solvable meltability copolyimide, is characterized in that the polymer repeat unit structure of this solvable meltability copolyimide is:
m:n=9～1:1～9
Preparation process comprises: polyamic acid preparation, chemical imidization and thermal treatment imidization, in polyamic acid preparation process, 1mol 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride and 0.1mol～0.9mol 4，4′-diaminodipohenyl ether and 0.9mol～0.1mol 1,4-Ursol D in room temperature reaction 3-5 hour, makes polyamic acid in dimethylacetamide solvent, then, in 100 weight parts of polyamide acid solutions, add 40～160 weight part dewatering agents, 5～50 weight part tertiary amines organic alkali catalysts and the appropriate nonpolar aromatic hydrocarbons of polyamic acid precipitation agent, violent stirring completes imidization for 0.5～2 hour, then, the copolyimide powder that filtration is separated out, with washing with acetone three times, filtration drying, obtain passing through the copolyimide molding powder in 100 mesh sieve holes, through 220 ℃～280 ℃ thermal treatment 2-3 hour, cause complete imidization, acquisition can be molded and shaped copolyimide molding powder, this molding powder has logarithmic viscosity number 40ml/g～110ml/g, this molding powder dissolves in N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone and Γ-butyrolactone, this molding powder is in 280～350 ℃, compression molding under 15～70MPa pressure, and clamp time, with variation in thickness, is generally 3～30min, moulded parts performance is:
Glass transition temperature Tg: 289 ℃～294 ℃
Weightless 5 % by weight temperature: 540 ℃～551 ℃
Weightless 10 % by weight temperature: 577 ℃～588 ℃
Tensile strength: 23 ℃, 114～120MPa tensile modulus: 23 ℃, 3.00～3.26GPa
220℃，46.4～50.3MPa 220℃，/
Flexural strength: 23 ℃, 151～156MPa modulus in flexure: 23 ℃, 2.90～3.09GPa
220℃，73.9～78.8MPa 220℃，2.06～2.13GPa
Compressive strength: 23 ℃, 156～161MPa modulus of compression: 23 ℃, 2.35～2.40GPa
220℃，63.0～65.4MPa 220℃，1.40～1.42GPa
Shock strength (non-notch): 23 ℃, 152～154J/m.
2. the preparation method of a kind of solvable meltability copolyimide according to claim 1, it is characterized in that in described polyamic acid preparation process, 1mol 2,3,3 ', 4 '-diphenyl ether tetraformic dianhydride reacts and is prepared from for 3～5 hours with 0.8～0.4mol 4，4′-diaminodipohenyl ether and 0.2～0.6mol Isosorbide-5-Nitrae-Ursol D in dimethylacetamide solvent.
3. the preparation method of a kind of solvable meltability copolyimide according to claim 1, is characterized in that m:n=8～4:2～6 in described polymer repeat unit structure formula.
4. the preparation method of a kind of solvable meltability copolyimide according to claim 1, is characterized in that this described molding powder has logarithmic viscosity number 50ml/g～80ml/g.
5. the preparation method of a kind of solvable meltability copolyimide according to claim 1, is characterized in that described dewatering agent is from aceticanhydride, propionic anhydride, to choose any one kind of them or their mixture.
6. the preparation method of a kind of solvable meltability copolyimide according to claim 1, it is characterized in that described tertiary amines organic alkali catalyst is from pyridine, 3, in the colony that 5-lutidine, N-toluquinoline, 3-picoline, tetramethyl pyridine, Trimethylamine 99, triethylamine and isoquinoline 99.9 form, choose any one kind of them or any two mixture.
7. the preparation method of a kind of solvable meltability copolyimide according to claim 1, it is characterized in that described appropriate nonpolar aromatic hydrocarbons polyimide precipitation agent is from toluene, dimethylbenzene, to choose any one kind of them or their mixture, 10～50 % by weight that its consumption is dimethylacetamide solvent.
8. the preparation method of a kind of solvable meltability copolyimide according to claim 1, is characterized in that described dimethylacetamide solvent take aromatic diamine 1mol as basis, and its consumption is 2200ml.
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| CN105131284A (en) * | 2015-07-16 | 2015-12-09 | 中国科学院化学研究所 | High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof |
| CN111234222A (en) * | 2020-01-15 | 2020-06-05 | 神马实业股份有限公司 | Preparation method of copolymerization modified thermosetting polyimide material |
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