CN101928460A - Preparation method of linear polyimide-maleimide copolymer film containing active groups - Google Patents
Preparation method of linear polyimide-maleimide copolymer film containing active groups Download PDFInfo
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- CN101928460A CN101928460A CN 201010256460 CN201010256460A CN101928460A CN 101928460 A CN101928460 A CN 101928460A CN 201010256460 CN201010256460 CN 201010256460 CN 201010256460 A CN201010256460 A CN 201010256460A CN 101928460 A CN101928460 A CN 101928460A
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Abstract
The invention relates to a preparation method of a linear polyimide-maleimide copolymer film containing active groups, which comprises the following steps of: (1) adding hydroxyl-contained aromatic di-primary amine and a strongly-polar aprotic organic solvent into a polymerization bottle, stirring at room temperature, cooling to the temperature below 5 DEG C through an ice-water bath, adding aromatic binary anhydride, stirring, and reacting to obtain a hydroxyl-contained aromatic polyamic acid resin solution; (2) dissolving maleimide resin into the strongly-polar aprotic organic solvent, and stirring and dissolving at the room temperature to obtain a maleimide resin solution; and (3) uniformly mixing the two solutions at the room temperature, regulating the viscosity, forming a film in a casting machine, carrying out chemical reactions, such as dehydrated thermal imidization, copolymerization and the like, cooling and de-filming to obtain the film. The preparation method has the advantages of mild reaction conditions, simple operation, low cost and environmental protection, is beneficial to realizing industrialized large-scale production and can be applied to high-technology fields of large-motor main insulating materials, electromagnetic wire-wound electric insulating materials, flexible copper-clad laminates and the like.
Description
Technical field
The invention belongs to the preparation field of Kapton, particularly relate to the preparation method who contains active group linear polyimide imines-maleimide copolymer film.
Background technology
Kapton is the very excellent macromolecular material of a class over-all properties, have excellent especially thermotolerance, lower temperature resistance, flame retardant resistance, electric property and mechanical property, be widely used in high-tech areas such as electronics microelectronics, printed circuit board, electric wire, generator stator winding insulation, boats and ships shipping, aerospace, laser, photoelectricity.
But, traditional Kapton, as KAPTON film and home-made H film that U.S. DUPONT company produces, their molecular structure is the pyromellitic acid anhydride type, be that its principal monomer raw material is pyromellitic acid anhydride and 4.
NASA (NASA) plans to launch the origin that space telescope of future generation (NGST) is used for further exploration of the universe in 2009, and wherein multilayer insulation sun visor material (MLI) is one of key material of realizing this plan.For this reason, but developed the novel polyimide film material of steady operation: LaRC under the space environment
TM-CP1 and LaRC
TM-CP2, its concrete molecular structure is as follows:
Its shortcoming is: (1) used starting material 2, and two (3,4-dicarboxyl phenyl) the hexafluoropropane dianhydride monomers of 2-are extremely expensive, cause the film product cost very high, seriously hindered it and further applied; (2) owing to 2, the reactive behavior of two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride monomers of 2-and aromatic dicarboxylic primary amine is low, be difficult to make the high-molecular weight polyimide resin, therefore, cause the over-all properties of its film product to descend greatly, particularly its mechanical property.
Japan NTT company also be utilize cost an arm and a leg, reactive behavior is low 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride monomer, with pyromellitic acid anhydride or 3,3 '-two (trifluoromethyl)-4,4 '-benzidine exploitation obtained in visible-range light transmission rate polyimide film material preferably.
People such as Yu Xinhai have done a large amount of research and developments to the polyimide monomer that is used to prepare Kapton: [new type polyimide is extraordinary monomeric synthetic and characterize (1), the insulating material communication, 1999,32 (5): 1-4] disclose 1, the preparation method of two (3-amino-benzene oxygen) benzene of 3-; (2) [3,3 '-the synthetic and polyimide of diaminodiphenyl oxide, insulating material, 2001,34 (4): 13-16] disclose 3,3 '-preparation method of diaminodiphenyl oxide; (3) [2, two [4-(3-amino-benzene oxygen) phenyl] preparation of propane and the researchs of soluble polyimide thereof of 2-, insulating material, 2001,34 (6): 3-6] disclose 2, the preparation method of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; (4) [the monomeric synthetic and application of bisphenol A-type polyimide, insulating material, 2002,35 (4): 3-7] and Chinese invention patent CN1472193A (2004-02-04) disclose 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; (5) [the synthetic and sign of the extraordinary body of fluorinated polyimide, New Chemical Materials, 2003,31 (10): 24-27,31] disclose 2, the preparation method of two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-; (6) [4,4 '-the synthetic and performance study of two (4-amino-benzene oxygen) diphenyl sulfides and polyimide thereof, insulating material, 2008,41 (5): 10-14] disclose 4,4 '-preparation method of two (4-amino-benzene oxygen) diphenyl sulfide.
The preparation method who contains active group linear polyimide imines-maleimide copolymer and film thereof disclosed in this invention does not see disclosed document or patent report as yet.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method who contains active group linear polyimide imines-maleimide copolymer film, this preparation method's reaction conditions gentleness, and reaction process is carried out under normal pressure, and is simple to operate; The reaction raw materials convenient sources, cost is low, does not relate to also not producing corrosives, and organic solvent uses the few and easy recovery of kind, and Recycling repeatedly is environmentally friendly; And this Kapton has excellent size stability, mechanical property and thermotolerance, and the Tonset temperature of its thermal weight loss collection of illustrative plates is up to 583.5 ℃.
A kind of preparation method who contains active group linear polyimide imines-maleimide copolymer film provided by the invention comprises:
(1) hydroxyl-contained aromatic di primary amine and strong polar non-proton organic solvent are added in the polymerization bottle, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to below 5 ℃, add aromatic dicarboxylic anhydride, stir, in 5 ℃-10 ℃ temperature range internal reactions after 3 hours, obtain homogeneous phase, transparent, thick hydroxyl aromatic polyamic acid resin solution; Wherein, the mole number of aromatic dicarboxylic anhydride equals the mole number of hydroxyl-contained aromatic di primary amine;
(2) maleimide resin is dissolved in the strong polar non-proton organic solvent, stirring and dissolving under the room temperature obtains the maleimide resin solution of homogeneous phase transparent;
(3) with hydroxyl aromatic polyamic acid resin solution and maleimide resin solution, mix under the room temperature, obtain homogeneous phase solution, regulate the viscosity of mixed solution with strong polar non-proton organic solvent, make its viscosity number (4# flow cup between-160 seconds that is in 80 seconds, 25 ℃), subsequently, mixed solution is film forming in casting machine, heat temperature raising carries out chemical reactions such as dehydration fever imidization and copolymerization, cooling, demoulding obtains to contain active group linear polyimide imines-maleimide copolymer film.Aromatic dicarboxylic anhydride in the described step (1) is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic phenyl ether dianhydride, 3,3 ', 4,4 '-the tetracarboxylic diphenyl sulfone dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 2, two (3, the 4-di carboxyl phenyloxy) the toluene dianhydrides of 6-, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 3-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy)-3,3 ' 5,5 '-the tetramethyl diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride and 4,4 '-in two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride one or more.
Hydroxyl-contained aromatic di primary amine in the described step (1) is selected from 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa and 2 of 2-, one or more in two (the 3-amino-4-hydroxy phenyl) propane of 2-.
Described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO).
Maleimide resin in the described step (2) is selected from 4,4 '-the dimaleoyl imino ditane, 4,4 '-the dimaleoyl imino phenyl ether, 4,4 '-the dimaleoyl imino sulfobenzide, 1,4-dimaleoyl imino benzene, 1,3-dimaleoyl imino benzene, 1,2-dimaleoyl imino benzene, 2,6-dimaleoyl imino toluene, 2,5-dimaleoyl imino toluene, 1, two (4-maleimide phenoxyl) benzene of 4-, 1, two (4-maleimide phenoxyl) benzene of 3-, 1, two (3-maleimide phenoxyl) benzene of 4-, 1, two (3-maleimide phenoxyl) benzene of 3-, 4,4 '-two (4-maleimide phenoxyl) biphenyl, 4,4 '-two (3-maleimide phenoxyl) biphenyl, 4,4 '-two (4-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-two (4-maleimide phenoxyl) phenyl ether, 4,4 '-two (4-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (3-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (4-maleimide phenoxyl) sulfobenzide, 4,4 '-two (3-maleimide phenoxyl) sulfobenzide, 4,4 '-two (4-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (3-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (4-maleimide phenoxyl) benzophenone, 4,4 '-two (3-maleimide phenoxyl) benzophenone, 2, two [4-(4-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(3-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(4-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(3-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-3-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(2-trifluoromethyl-3-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) benzophenone, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) benzophenone, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) phenyl ether, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) phenyl ether, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) sulfobenzide, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) sulfobenzide, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) biphenyl, 1, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 3-, 1, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, 1, two (2-trifluoromethyl-3-maleimide phenoxyl) benzene of 3-, 1, two (2-trifluoromethyl-3-maleimide phenoxyl) benzene of 4-, 2, two (2-trifluoromethyl-4-maleimide phenoxyl) toluene of 6-, 2, two (2-trifluoromethyl-4-maleimide phenoxyl) toluene of 5-, 1, two (2, the 4-dimaleimide phenoxyl) benzene of 4-, 1,3-two (2,4-dimaleimide phenoxyl) benzene, 1, two (2, the 4-dimaleimide phenoxyl) benzene of 2-, 2,2-is two, and [4-(2,4-dimaleimide phenoxyl) phenyl] propane, 2, two [4-(2, the 4-dimaleimide phenoxyl) phenyl] HFC-236fa of 2-, 4,4 '-two (2,4-dimaleimide phenoxyl) phenyl ether, 4,4 '-two (2,4-dimaleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2,4-dimaleimide phenoxyl) biphenyl, 4,4 '-two (2,4-dimaleimide phenoxyl) sulfobenzide, 4,4 '-two (2,4-dimaleimide phenoxyl) benzophenone, in the N-phenylmaleimide one or more.
The temperature range of described dehydration fever imidization and copolyreaction is between 100 ℃-300 ℃.
The solid content of the hydroxyl aromatic polyamic acid resin solution in the described step (1) is 10wt%-15wt% (weight).
The solid content of the maleimide resin solution in the described step (2) is 20wt%-30wt% (weight).
Hydroxyl aromatic polyamic acid resin solution in the described step (3) and maleimide resin solution blended ratio are 1: the mass ratio of 0.1-2.0.
Beneficial effect
(1) preparation method's reaction conditions gentleness of the present invention, reaction process is carried out under normal pressure, and is simple to operate; The reaction raw materials convenient sources, cost is low, does not relate to also not producing corrosives, and organic solvent uses the few and easy recovery of kind, and Recycling repeatedly is environmentally friendly;
(2) the used synthesis technique equipment of preparation process is universal, can utilize the suite of equipment of existing production polyimide resin to implement the present invention fully, is very beneficial for the industrialization of product;
(3) production unit of the present invention is general Kapton production unit, promptly general casting machine, and facility investment is few, is very beneficial for enforcement of the present invention;
(4) the material resin molecular weight of Cai Yonging is controlled easily, molecular structure is also adjusted easily, help preparing the water white Kapton of ideal performance, and this Kapton has excellent size stability, mechanical property and thermotolerance, and the Tonset temperature of its thermal weight loss collection of illustrative plates is up to 583.5 ℃;
(5) the active group linear polyimide imines-maleimide copolymer film that contains provided by the invention can be applicable to big generator stator winding insulation, the wrapped insulating material of insulated wire, flexible copper clad foil plate high-tech areas such as (FCCL).
Description of drawings
Fig. 1 is thermogravimetic analysis (TGA) (TGA) collection of illustrative plates that contains active group linear polyimide imines-maleimide copolymer film of embodiment 1;
Fig. 2 is thermogravimetic analysis (TGA) (TGA) collection of illustrative plates that contains active group linear polyimide imines-maleimide copolymer film of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
With 21.6 gram (0.1 moles) 3,3 '-diamino-4,4 '-the hydroxyl-contained aromatic di primary amine of dihydroxybiphenyl and 432.0 gram N, the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE adds in the polymerization bottle, stir under the room temperature, after the dissolving, ice-water bath is cooled to below 5 ℃ fully, adds 10.9 gram (0.05 mole) pyromellitic acid anhydrides and 15.5 gram (0.05 moles) 3,3 ', 4,4 '-aromatic dicarboxylic anhydride of tetracarboxylic phenyl ether dianhydride, stir, in 5 ℃-10 ℃ temperature range internal reactions after 3 hours, obtain homogeneous phase, transparent, thick hydroxyl aromatic polyamic acid resin solution, solid content is 10wt%, note is made the HPAA-1 resin liquid;
With 72.0 grams 1,4-two (2,4-dimaleimide phenoxyl) benzene, 100.0 restrain 2, two [4-(4-maleimide phenoxyl) phenyl] propane of 2-and 20.0 grams 4,4 '-maleimide resin of dimaleoyl imino ditane is dissolved in 768.0 gram N, in the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE, stirring and dissolving under the room temperature, obtain 1 of homogeneous phase transparent, two (2, the 4-dimaleimide phenoxyl) benzene of 4-, 2, two [4-(4-maleimide phenoxyl) phenyl] propane and 4 of 2-, 4 '-the maleimide resin solution of dimaleoyl imino ditane, solid content is 20wt%, note is made the MI-1 resin liquid;
With HPAA-1 hydroxyl aromatic polyamic acid resin solution and MI-1 maleimide resin solution, under the room temperature, mass ratio by 1: 2 mixes, obtain homogeneous phase solution, add 80.0 gram N, the viscosity that the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE is regulated mixed solution, stir under the room temperature, surveying its viscosity number is 86 seconds (4# flow cup, 25 ℃), subsequently, mixed solution is film forming in casting machine, and heat temperature raising carries out chemical reactions such as dehydration fever imidization and copolymerization in 100 ℃ of-300 ℃ of temperature ranges, cooling, demoulding obtains to contain active group linear polyimide imines-maleimide copolymer film, and note is made the HPIMI-1 film, its thermal weight loss (TGA) collection of illustrative plates as shown in Figure 1, the Tonset temperature is up to 583.5 ℃; Tensile strength is 152MPa; Elongation at break is 6.2%; Volume specific resistance is 3.7 * 10
14Ω cm; Water-intake rate is 0.7%.
With 21.6 gram (0.1 moles) 3,3 '-diamino-4,4 '-dihydroxybiphenyl and 36.6 gram (0.1 moles) 2, hydroxyl-contained aromatic di primary amine of two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-and 277.2 gram N-N-methyl-2-2-pyrrolidone N-s and 300.0 gram N, the strong polar non-proton organic solvent of N-N,N-DIMETHYLACETAMIDE adds in the polymerization bottle, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to below 5 ℃, the aromatic dicarboxylic anhydride that adds 43.6 gram (0.2 mole) pyromellitic acid anhydrides, stir, in 5 ℃-10 ℃ temperature range internal reactions after 3 hours, obtain homogeneous phase, transparent, thick hydroxyl aromatic polyamic acid resin solution, solid content is 15wt%, note is made the HPAA-2 resin liquid;
With 21.0 grams 4,4 '-maleimide resin of dimaleoyl imino ditane is dissolved in the strong polar non-proton organic solvent of 49.0 gram N-N-methyl-2-2-pyrrolidone N-s, stirring and dissolving under the room temperature, obtain 4 of homogeneous phase transparent, 4 '-the maleimide resin solution of dimaleoyl imino ditane, solid content is 30wt%, and note is made the MI-2 resin liquid;
With HPAA-2 hydroxyl aromatic polyamic acid resin solution and MI-2 maleimide resin solution, under the room temperature, mass ratio by 1: 0.1 mixes, obtain homogeneous phase solution, add the viscosity that the strong polar non-proton organic solvent of 150.0 gram N-N-methyl-2-2-pyrrolidone N-s is regulated mixed solution, stir under the room temperature, surveying its viscosity number is 154 seconds (4# flow cups, 25 ℃), subsequently, mixed solution is film forming in casting machine, heat temperature raising, in 100 ℃ of-300 ℃ of temperature ranges, carry out chemical reactions such as dehydration fever imidization and copolymerization, cooling, demoulding, acquisition contains active group linear polyimide imines-maleimide copolymer film, note is made the HPIMI-2 film, its thermal weight loss (TGA) collection of illustrative plates as shown in Figure 2, the Tonset temperature is up to 571.8 ℃; Tensile strength is 137MPa; Elongation at break is 12.9%; Volume specific resistance is 2.4 * 10
14Ω cm; Water-intake rate is 0.9%.
Claims (9)
1. preparation method who contains active group linear polyimide imines-maleimide copolymer film comprises:
(1) hydroxyl-contained aromatic di primary amine and strong polar non-proton organic solvent are added in the polymerization bottle, stir under the room temperature, fully after the dissolving, ice-water bath is cooled to below 5 ℃, add aromatic dicarboxylic anhydride, stir, in 5 ℃-10 ℃ temperature range internal reactions after 3 hours, obtain homogeneous phase, transparent, thick hydroxyl aromatic polyamic acid resin solution; Wherein, the mole number of aromatic dicarboxylic anhydride equals the mole number of hydroxyl-contained aromatic di primary amine;
(2) maleimide resin is dissolved in the strong polar non-proton organic solvent, stirring and dissolving under the room temperature obtains the maleimide resin solution of homogeneous phase transparent;
(3) with hydroxyl aromatic polyamic acid resin solution and maleimide resin solution, mix under the room temperature, obtain homogeneous phase solution, the viscosity with strong polar non-proton organic solvent is regulated mixed solution makes its viscosity number be in 80 seconds between-160 seconds, subsequently, mixed solution is film forming in casting machine, and heat temperature raising carries out dehydration fever imidization and copolyreaction, cooling, demoulding obtains to contain active group linear polyimide imines-maleimide copolymer film.
2. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1, it is characterized in that: the aromatic dicarboxylic anhydride in the described step (1) is selected from pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic phenyl ether dianhydride, 3,3 ', 4,4 '-the tetracarboxylic diphenyl sulfone dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2-, 2,6-two (3, the 4-di carboxyl phenyloxy) toluene dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-, 1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3,5 the 4-di carboxyl phenyloxy)-3,3 ' 5, '-the tetramethyl diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride and 4,4 '-in two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride one or more.
3. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1, it is characterized in that: the hydroxyl-contained aromatic di primary amine in the described step (1) is selected from 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa and 2 of 2-, one or more in two (the 3-amino-4-hydroxy phenyl) propane of 2-.
4. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1, it is characterized in that: described strong polar non-proton organic solvent is selected from N, in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO) one or more.
5. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1, it is characterized in that: the maleimide resin in the described step (2) is selected from 4,4 '-the dimaleoyl imino ditane, 4,4 '-the dimaleoyl imino phenyl ether, 4,4 '-the dimaleoyl imino sulfobenzide, 1,4-dimaleoyl imino benzene, 1,3-dimaleoyl imino benzene, 1,2-dimaleoyl imino benzene, 2,6-dimaleoyl imino toluene, 2,5-dimaleoyl imino toluene, 1, two (4-maleimide phenoxyl) benzene of 4-, 1, two (4-maleimide phenoxyl) benzene of 3-, 1, two (3-maleimide phenoxyl) benzene of 4-, 1, two (3-maleimide phenoxyl) benzene of 3-, 4,4 '-two (4-maleimide phenoxyl) biphenyl, 4,4 '-two (3-maleimide phenoxyl) biphenyl, 4,4 '-two (4-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl biphenyl, 4,4 '-two (4-maleimide phenoxyl) phenyl ether, 4,4 '-two (4-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (3-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (4-maleimide phenoxyl) sulfobenzide, 4,4 '-two (3-maleimide phenoxyl) sulfobenzide, 4,4 '-two (4-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (3-maleimide phenoxyls)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (4-maleimide phenoxyl) benzophenone, 4,4 '-two (3-maleimide phenoxyl) benzophenone, 2, two [4-(4-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(3-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(4-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(3-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-3-maleimide phenoxyl) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 2, two [4-(2-trifluoromethyl-3-maleimide phenoxyl) phenyl] HFC-236fa of 2-, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) benzophenone, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) benzophenone, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) phenyl ether, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) phenyl ether, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) sulfobenzide, 4,4 '-two (2-trifluoromethyl-3-maleimide phenoxyl) sulfobenzide, 4,4 '-two (2-trifluoromethyl-4-maleimide phenoxyl) biphenyl, 1, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 3-, 1, two (2-trifluoromethyl-4-maleimide phenoxyl) benzene of 4-, 1, two (2-trifluoromethyl-3-maleimide phenoxyl) benzene of 3-, 1, two (2-trifluoromethyl-3-maleimide phenoxyl) benzene of 4-, 2, two (2-trifluoromethyl-4-maleimide phenoxyl) toluene of 6-, 2, two (2-trifluoromethyl-4-maleimide phenoxyl) toluene of 5-, 1,4-two (2,4-dimaleimide phenoxyl) benzene, 1, two (2, the 4-dimaleimide phenoxyl) benzene of 3-, 1,2-two (2,4-dimaleimide phenoxyl) benzene, 2, two [4-(2, the 4-dimaleimide phenoxyl) phenyl] propane of 2-, 2,2-is two, and [4-(2,4-dimaleimide phenoxyl) phenyl] HFC-236fa, 4,4 '-two (2,4-dimaleimide phenoxyl) phenyl ether, 4,4 '-two (2,4-dimaleimide phenoxyl) diphenyl sulfide, 4,4 '-two (2,4-dimaleimide phenoxyl) biphenyl, 4,4 '-two (2,4-dimaleimide phenoxyl) sulfobenzide, 4,4 '-two (2,4-dimaleimide phenoxyl) benzophenone, in the N-phenylmaleimide one or more.
6. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1 is characterized in that: the temperature range of described dehydration fever imidization and copolyreaction is between 100 ℃-300 ℃.
7. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1 is characterized in that: the solid content of the hydroxyl aromatic polyamic acid resin solution in the described step (1) is 10wt%-15wt%.
8. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1 is characterized in that: the solid content of the maleimide resin solution in the described step (2) is 20wt%-30wt%.
9. the preparation method who contains active group linear polyimide imines-maleimide copolymer film according to claim 1 is characterized in that: hydroxyl aromatic polyamic acid resin solution in the described step (3) and maleimide resin solution blended ratio are 1: the mass ratio of 0.1-2.0.
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| CN 201010256460 CN101928460B (en) | 2010-08-18 | 2010-08-18 | Preparation method of linear polyimide-maleimide copolymer film containing active groups |
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| CN 201010256460 CN101928460B (en) | 2010-08-18 | 2010-08-18 | Preparation method of linear polyimide-maleimide copolymer film containing active groups |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509576A (en) * | 2011-09-29 | 2012-06-20 | 东华大学 | High-vacuum-resistant high-temperature-resistant wire cable and preparation method thereof |
| CN102516867A (en) * | 2011-12-14 | 2012-06-27 | 东华大学 | Polyimide paint for optical fiber and preparation method thereof |
| CN105176078A (en) * | 2015-08-11 | 2015-12-23 | 东华大学 | Electroplating biphenyl type maleimido polyimide modified engineering plastic alloy and preparation method thereof |
| CN108948354A (en) * | 2017-05-26 | 2018-12-07 | 昆山国显光电有限公司 | Modified polyimide resin and preparation method thereof and application |
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| JP2000223805A (en) * | 1999-02-03 | 2000-08-11 | Tomoegawa Paper Co Ltd | Laminate material for circuit |
| CN1548474A (en) * | 2003-05-07 | 2004-11-24 | 上海金山前峰绝缘材料有限公司 | Prepn of polyimide film for copper to be clad on |
| CN1927908A (en) * | 2006-09-05 | 2007-03-14 | 东华大学 | Preparation method of phenolic hydroxyl group containing polyimide powder |
| CN101541888A (en) * | 2006-10-04 | 2009-09-23 | 三菱瓦斯化学株式会社 | Two-part thermocurable polyimide resin composition and cured product thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000223805A (en) * | 1999-02-03 | 2000-08-11 | Tomoegawa Paper Co Ltd | Laminate material for circuit |
| CN1548474A (en) * | 2003-05-07 | 2004-11-24 | 上海金山前峰绝缘材料有限公司 | Prepn of polyimide film for copper to be clad on |
| CN1927908A (en) * | 2006-09-05 | 2007-03-14 | 东华大学 | Preparation method of phenolic hydroxyl group containing polyimide powder |
| CN101541888A (en) * | 2006-10-04 | 2009-09-23 | 三菱瓦斯化学株式会社 | Two-part thermocurable polyimide resin composition and cured product thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509576A (en) * | 2011-09-29 | 2012-06-20 | 东华大学 | High-vacuum-resistant high-temperature-resistant wire cable and preparation method thereof |
| CN102509576B (en) * | 2011-09-29 | 2014-05-28 | 东华大学 | High-vacuum-resistant high-temperature-resistant wire cable and preparation method thereof |
| CN102516867A (en) * | 2011-12-14 | 2012-06-27 | 东华大学 | Polyimide paint for optical fiber and preparation method thereof |
| CN105176078A (en) * | 2015-08-11 | 2015-12-23 | 东华大学 | Electroplating biphenyl type maleimido polyimide modified engineering plastic alloy and preparation method thereof |
| CN105176078B (en) * | 2015-08-11 | 2017-08-01 | 东华大学 | A kind of polyimide modified engineering plastic alloy of electrodepositable biphenyl type dimaleoyl imino and preparation method thereof |
| CN108948354A (en) * | 2017-05-26 | 2018-12-07 | 昆山国显光电有限公司 | Modified polyimide resin and preparation method thereof and application |
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| CN101928460B (en) | 2012-07-04 |
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