CN100412111C - Preparation method of phenolic hydroxyl group containing polyimide powder - Google Patents
Preparation method of phenolic hydroxyl group containing polyimide powder Download PDFInfo
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- CN100412111C CN100412111C CNB2006100308272A CN200610030827A CN100412111C CN 100412111 C CN100412111 C CN 100412111C CN B2006100308272 A CNB2006100308272 A CN B2006100308272A CN 200610030827 A CN200610030827 A CN 200610030827A CN 100412111 C CN100412111 C CN 100412111C
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Abstract
The preparation process of phenolic hydroxyl group-containing polyimide powder includes the following steps: 1. reaction of phenolic hydroxyl group-containing aromatic diamine compound or its mixture with other diamine compound and aromatic binary anhydride in the molar ratio of 1 to 1 in strong polar non-protonic organic solvent under protection of nitrogen at 0-30 deg.c for 3-12 hr to obtain transparent ropy polyhydroxy amido acid solution; and 2. adding azeotropic dewatering agent in nitrogen atmosphere and heating to 120-160 deg.c to reflux, azeotropically dewater and imidize for 5-18 hr, cooling to room temperature, washing and vacuum drying to obtain phenolic hydroxyl group-containing polyimide powder. The industrial production process has environment friendship, simple operation, low cost and easy solvent recovery.
Description
Technical field
The present invention relates to a kind of preparation method who contains the fire-resistant high-performance aromatic heterocyclic polymer powder of active phenolic hydroxyl group reactive group, particularly relate to a kind of preparation method of phenolic hydroxy group polyimide powder.
Background technology
Polyimide is the very excellent polymkeric substance of a class over-all properties, has very good thermotolerance, lower temperature resistance, solvent resistance, self lubricity, radiation resistance and characteristic such as fire-retardant, simultaneously, also has very excellent mechanical property and dielectric properties.Therefore, it is widely used in the high temperature resistant radiation hardness material of spaceship, satellite or space craft etc.; The advanced configuration matrix material of aspects such as aerospace, automobile, electromechanics, C level or 200 higher level insulating materials, high-temperature resistance adhesive etc.; And interlayer dielectic, super large-scale integration passivating coating and the alpha-particle blocking layer coating material etc. of the body material of the FPC of electronics microelectronic or PCB, IC.
U.S. Pat 5147966 discloses a kind of preparation method of polyimide powder, be primarily characterized in that: with diglyme (diglyme) is solvent, make 3,4 '-diaminodiphenyl oxide (34ODA) and 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA) and Tetra hydro Phthalic anhydride (PA) at room temperature react, after obtaining polyamic acid solution, add N-N-methyl-2-2-pyrrolidone N-(NMP), triethylamine (TEA) and diacetyl oxide (Ac
2O) carry out chemical imidization reaction, add that depositing in water is analysed, filters, washed, drying, obtain polyimide powder.
Chemical equation is as follows:
The shortcoming of this method is: (1) uses triethylamine/diacetyl oxide system to carry out imidization, the production cost height, and irritating smell is big, makes troubles to operation, also pollutes to environment; (2) organic solvent separates, the recycle and reuse difficulty is big, the processing costs height; (3) add operations such as depositing in water is analysed, washing and produce a large amount of waste water, the wastewater treatment difficulty is big and expense is high.
Because phenolic hydroxyl group is easy and diacetyl oxide generation esterification, so the method for US5147966 very is not suitable for preparing the polyimide powder of phenolic hydroxy group.If come chemical imidization to prepare the phenolic hydroxy group polyimide powder, then must also to carry out the hydrolysis reaction of ester group, to obtain phenolic hydroxyl group again with triethylamine/diacetyl oxide system.This can increase problems such as the cost and the three wastes undoubtedly.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of phenolic hydroxy group polyimide powder, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of phenolic hydroxy group polyimide powder comprises the steps:
(1) mol ratio is that the mixture of 1: 1 phenolic hydroxy group aromatic dicarboxylic amine compound or phenolic hydroxy group aromatic diamine and other diamine and aromatic dicarboxylic acid anhydride are in strong polar non-proton organic solvent, under the nitrogen protection, after reacting 3～12 hours under 0 ℃～30 ℃, obtain transparent heavy-gravity polyhydroxyamide acid solution, wherein, to account for the mass percent of whole reaction system be 5%～30% to strong polar non-proton organic solvent;
(2) in the nitrogen atmosphere, add azeotropy dehydrant, heat temperature raising is in 120 ℃～160 ℃ temperature range, backflow azeotropic dehydration imidization 5～18 hours, be cooled to room temperature, filter, washing, vacuum-drying, obtain the phenolic hydroxy group polyimide powder, wherein, azeotropy dehydrant is 0.1～10: 1 with the volume ratio of strong polar non-proton organic solvent.
As optimized technical scheme: described phenolic hydroxy group aromatic dicarboxylic amine compound is 4 "-hydroxy phenyl-4; 4 '-diaminodiphenylmethane (HPDDM); 3 "-hydroxy phenyl-4,4 '-diaminodiphenylmethane (3HPDDM), 2, two (the 3-amino-4-hydroxy phenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa (B3A4HPFP), 2, two (the 3-hydroxyls-4-aminophenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa (B3H4APFP), 2, two (the 3-amino-4-hydroxy phenyl) propane (B3A4HPP) of 2-, 2, two (3-hydroxyl-4-aminophenyl) propane (B3H4APP) of 2-, 3,3 '-diamino-4,4 '-dihydroxybiphenyl (B3A4HBP), 3,3 '-dihydroxyl-4,4 '-benzidine (B3H4ABP), 3,3 '-diamino-4,4 '-dioxydiphenyl methane (3A4HDPM), 3,3 '-dihydroxyl-4,4 '-diaminodiphenylmethane (3H4ADPM), 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone (3A4HDPS), 3,3 '-dihydroxyl-4,4 '-diaminodiphenylsulfone(DDS) (3H4ADPS), 3,3 '-diamino-4,4 '-dihydroxyl diphenyl sulfide (3A4HDPSE), 3,3 '-dihydroxyl-4,4 '-diaminodiphenyl sulfide (3H4ADPSE), 3,3 '-diamino-4,4 '-dihydroxy diphenyl ether (3A4HDPE), 3,3 '-dihydroxyl-4,4 '-diaminodiphenyl oxide (3H4ADPE), 4, one or more in the 6-diamino resorcin (46DAR).
Described other diamine is quadrol (EDA), 1,3-propylene diamine (13PDA), 1,2-propylene diamine (12PDA), 1,4-butanediamine (14BDA), 1,6-hexanediamine (16HDA), mphenylenediamine (mPDA), O-Phenylene Diamine (oPDA), Ursol D (pPDA), 4,4 '-benzidine (Bz), 3,3 '-dimethyl-4,4 '-benzidine (TLD), 3,3 '-dimethoxy-4 ', 4 '-benzidine (DMOBZ), 4,4 '-diaminodiphenylmethane (MDA), 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane (DMOMDA), 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane (DMMDA), 3,3 '-two chloro-4,4 '-diaminodiphenylmethane (DCMDA), 4,4 '-diaminodiphenyl oxide (ODA), 3,4 '-diaminodiphenyl oxide (34ODA), 3,3 '-diaminodiphenyl oxide (33ODA), 4,4 '-diaminodiphenyl sulfide (DADPSE), 4,4 '-diaminodiphenylsulfone(DDS) (DADPS), 3,3 '-diaminodiphenylsulfone(DDS) (33DADPS), 4,4 '-diaminobenzophenone (DABP), 3,3 '-diaminobenzophenone (33DABP), 1, two (3-amino-benzene oxygen) benzene (133BAPB) of 3-, 1, two (4-amino-benzene oxygen) benzene (134BAPB) of 3-, 1, two (3-amino-benzene oxygen) benzene (143BAPB) of 4-, 1, two (4-amino-benzene oxygen) benzene (144BAPB) of 4-, 1, two (3-amino-benzene oxygen) benzene (123BAPB) of 2-, 1, two (4-amino-benzene oxygen) benzene (124BAPB) of 2-, 4,4 '-two (4-amino-benzene oxygen) phenyl ether (B4APDPE), 4,4 '-two (3-amino-benzene oxygen) phenyl ether (B3APDPE), 4,4 '-two (4-amino-benzene oxygen) benzophenone (B4APBP), 4,4 '-two (3-amino-benzene oxygen) benzophenone (B3APBP), 4,4 '-two (4-amino-benzene oxygen) ditanes (B4APDDM), 4,4 '-two (3-amino-benzene oxygen) ditanes (B3APDDM), 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfides (B4APDPSE), 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfides (B3APDPSE), 4,4 '-two (4-amino-benzene oxygen) sulfobenzides (B4APDPS), 4,4 '-two (3-amino-benzene oxygen) sulfobenzides (B3APDPS), 4,4 '-two (4-amino-benzene oxygen) biphenyl (B4APOBP), 4,4 '-two (3-amino-benzene oxygen) biphenyl (B4APOBP), 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane (3BAPP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPFP) of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa (3BAPFP) of 2-, 2, one or more in two (4-aminophenyl) HFC-236fa (BAPHFP) of 2-.
Described aromatic dicarboxylic acid anhydride is pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA), 2,3,3 ', 4 '-tetracarboxylic acid phenyl ether dianhydride (2334ODPA), 2,2 ', 3,3 '-tetracarboxylic acid phenyl ether dianhydride (2233ODPA), 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA), 2,3,3 ', 4 '-tetracarboxylic acid benzophenone dianhydride (2334BTDA), 2,2 ', 3,3 '-tetracarboxylic acid benzophenone dianhydride (2233BTDA), 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride (BPDA), 2,3,3 ', 4 '-tetracarboxylic acid biphenyl dianhydride (2334BPDA), 2,2 ', 3,3 '-tetracarboxylic acid biphenyl dianhydride (2233BPDA), 3,3 ', 4,4 '-tetracarboxylic acid diphenyl sulfone dianhydride (DSDA), 2,3,3 ', 4 '-tetracarboxylic acid diphenyl sulfone dianhydride (2334DSDA), 2,2 ', 3,3 '-tetracarboxylic acid diphenyl sulfone dianhydride (2233DSDA), 3,3 ', 4,4 '-tetracarboxylic acid diphenyl sulfide dianhydride (SDPA), 2,3,3 ', 4 '-tetracarboxylic acid diphenyl sulfide dianhydride (2334SDPA), 2,2 ', 3,3 '-tetracarboxylic acid diphenyl sulfide dianhydride (2233SDPA), 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride (6FDA), 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides (HQDA) of 4-, 1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride (ResDA), 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides (OPDDA) of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA), 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides (BPAFDA) of 2-, 1,4,5, in the 8-naphthalenetetracarbacidic acidic dianhydride (NTDA)-kind or several.
Described strong polar non-proton organic solvent is N, one or more in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), the dimethyl sulfoxide (DMSO) (DMSO).
Azeotropy dehydrant described in the step (2) is one or more in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene, preferred toluene.
Chemical equation of the present invention is as follows:
Wherein, m, n, p, q are not less than zero integer, and m and n can not equal zero q=m+n+p simultaneously;
A is the integer greater than 1.
The invention has the beneficial effects as follows: (1) the present invention is the commercial run of preparation phenolic hydroxy group polyimide powder; (2) three wastes are few, environmental friendliness; (3) simple to operate, equipment there is not particular requirement, less investment can be finished the operating process of preparation phenolic hydroxy group polyimide powder in same reactor; (4) solvent recuperation is easy, and reusable edible, and product cost is reduced, and also helps environment protection; (5) phenolic hydroxyl group does not participate in reaction in the whole process of preparation, is favourable to the cost that reduces product.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
With 25.8 gram (0.1 moles) 2, two (the 3-amino-4-hydroxy phenyl) propane (B3A4HPP) of 2-are added in the polymerization bottle, add 400 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP), feed nitrogen, ice-water bath is cooled to 5 ℃, stirs, after making it to dissolve fully, add 21.8 gram (0.1 mole) pyromellitic acid anhydride (PMDA) powder, stirring reaction obtained thick poly-adjacent oxyamide acid solution after 3 hours.Subsequently, feed nitrogen, add 40 milliliters of toluene, heat temperature raising is to refluxing, and 140 ℃ kept 18 hours.Have the yellow solid powder to separate out in the reaction flask, close heating system, stir fast, naturally cool to room temperature after, filter, washing obtains the phenolic hydroxy group polyimide powder.Infrared spectra absorbs in the spectrogram tangible OH absorption peak (3400cm
-1), the charateristic avsorption band of imide ring: 1776cm
-1And 1716cm
-1
Embodiment 2
With 25.8 gram (0.1 moles) 2, two (the 3-amino-4-hydroxy phenyl) propane (B3A4HPP) of 2-are added in the polymerization bottle, add 450 milliliters of N-N-methyl-2-2-pyrrolidone N-s (NMP), feed nitrogen, ice-water bath is cooled to 5 ℃, stir, after making it to dissolve fully, add 10.9 gram (0.05 mole) pyromellitic acid anhydride (PMDA) powder and 14.7 gram (0.05 moles) 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride (BPDA) powder, behind the stirring reaction 3 hours, obtain thick poly-adjacent oxyamide acid solution.Subsequently, feed nitrogen, add 500 milliliters of toluene, heat temperature raising 160 ℃, keeps steaming part toluene after 5 hours to refluxing.Have the yellow solid powder to separate out in the reaction flask, close heating system, stir fast, naturally cool to room temperature after, filter, washing obtains the phenolic hydroxy group polyimide powder.
Embodiment 3
With 12.9 gram (0.05 moles) 2, two (3-amino-4-hydroxy phenyl) propane (B3A4HPP) of 2-and 18.3 gram (0.05 moles) 2, two (the 3-amino-4-hydroxy phenyl)-1,1 of 2-, 1,3,3,3-HFC-236fa (B3A4HPFP) is added in the polymerization bottle, add 400 milliliters of N, N-N,N-DIMETHYLACETAMIDE (DMAc) feeds nitrogen, and ice-water bath is cooled to 0 ℃, stir, after making it to dissolve fully, add 10.9 (0.05 moles) gram pyromellitic acid anhydride (PMDA) powder and 14.7 gram (0.05 moles) 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride (BPDA) powder, stirring reaction obtained thick poly-adjacent oxyamide acid solution after 12 hours.Subsequently, feed nitrogen, add 600 milliliters of toluene, heat temperature raising is to refluxing, and 120 ℃ keep steaming part toluene after 5 hours.Have the yellow solid powder to separate out in the reaction flask, close heating system, stir fast, naturally cool to room temperature after, filter, washing obtains the phenolic hydroxy group polyimide powder.
Embodiment 4
Remove and adopt 31.0 gram (0.1 moles) 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA) powder replaces 21.8 gram (0.1 mole) pyromellitic acid anhydride (PMDA) powder and 800 milliliters of dimethylbenzene to replace outside 40 milliliters of toluene, and other raw material, prescription, technology are all with embodiment 1.Finally also obtain the phenolic hydroxy group polyimide powder.
Embodiment 5
Remove and adopt 32.2 gram (0.1 moles) 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA) powder to replace outside 21.8 gram (0.1 mole) pyromellitic acid anhydride (PMDA) powder, other raw material, prescription, technology are all with embodiment 1.Finally also obtain the phenolic hydroxy group polyimide powder.
Embodiment 6
Remove and adopt 52.0 gram (0.1 moles) 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride (BPADA) powder of 2-to replace outside 21.8 gram (0.1 mole) pyromellitic acid anhydride (PMDA) powder, other raw material, prescription, technology are all with embodiment 1.Finally also obtain the phenolic hydroxy group polyimide powder.
Claims (7)
1. the preparation method of a phenolic hydroxy group polyimide powder, it is characterized in that, comprise the steps: that (1) mol ratio is that the mixture of 1: 1 phenolic hydroxy group aromatic dicarboxylic amine compound or phenolic hydroxy group aromatic diamine and other diamine and aromatic dicarboxylic acid anhydride are in strong polar non-proton organic solvent, under the nitrogen protection, after reacting 3～12 hours under 0 ℃～30 ℃, obtain transparent heavy-gravity polyhydroxyamide acid solution, wherein, to account for the mass percent of whole reaction system be 5%～30% to strong polar non-proton organic solvent;
(2) in the nitrogen atmosphere, add azeotropy dehydrant, heat temperature raising is in 120 ℃～160 ℃ temperature range, backflow azeotropic dehydration imidization 5～18 hours, be cooled to room temperature, filter, washing, vacuum-drying, obtain the phenolic hydroxy group polyimide powder, wherein, azeotropy dehydrant is 0.1～10: 1 with the volume ratio of strong polar non-proton organic solvent.
2. preparation method according to claim 1, it is characterized in that described phenolic hydroxy group aromatic dicarboxylic amine compound is 4 '-hydroxy phenyl-4,4 '-diaminodiphenylmethane, 3 '-hydroxy phenyl-4,4 '-diaminodiphenylmethane, 2, two (the 3-amino-4-hydroxy phenyl)-1,1,1 of 2-, 3,3, the 3-HFC-236fa, 2, two (the 3-hydroxyls-4-aminophenyl)-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (3-hydroxyl-4-aminophenyl) propane of 2-, 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-diamino-4,4 '-dioxydiphenyl methane, 3,3 '-dihydroxyl-4,4 '-diaminodiphenylmethane, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3,3 '-dihydroxyl-4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diamino-4,4 '-dihydroxyl diphenyl sulfide, 3,3 '-dihydroxyl-4,4 '-diaminodiphenyl sulfide, 3,3 '-diamino-4,4 '-dihydroxy diphenyl ether, 3,3 '-dihydroxyl-4,4 '-diaminodiphenyl oxide, 4, one or more in the 6-diamino resorcin.
3. preparation method according to claim 1, it is characterized in that, described other diamine is a quadrol, 1, the 3-propylene diamine, 1, the 2-propylene diamine, 1, the 4-butanediamine, 1, the 6-hexanediamine, mphenylenediamine, O-Phenylene Diamine, Ursol D, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 4,4 '-diaminodiphenylmethane, 3,3 '-dimethoxy-4 ', 4 '-diaminodiphenylmethane, 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane, 3,3 '-two chloro-4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (3-amino-benzene oxygen) benzene of 2-, 1, two (4-amino-benzene oxygen) benzene of 2-, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) ditane, 4,4 '-two (3-amino-benzene oxygen) ditane, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, one or more in two (4-aminophenyl) HFC-236fa of 2-.
4. preparation method according to claim 1 is characterized in that, described aromatic dicarboxylic acid anhydride is a pyromellitic acid anhydride, 3,3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride, 2,3,3 ', 4 '-tetracarboxylic acid phenyl ether dianhydride, 2,2 ', 3,3 '-tetracarboxylic acid phenyl ether dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, 2,3,3 ', 4 '-tetracarboxylic acid benzophenone dianhydride, 2,2 ', 3,3 '-tetracarboxylic acid benzophenone dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid biphenyl dianhydride, 2,3,3 ', 4 '-tetracarboxylic acid biphenyl dianhydride, 2,2 ', 3,3 '-tetracarboxylic acid biphenyl dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid diphenyl sulfone dianhydride, 2,3,3 ', 4 '-tetracarboxylic acid diphenyl sulfone dianhydride, 2,2 ', 3,3 '-tetracarboxylic acid diphenyl sulfone dianhydride, 3,3 ', 4,4 '-tetracarboxylic acid diphenyl sulfide dianhydride, 2,3,3 ', 4 '-tetracarboxylic acid diphenyl sulfide dianhydride, 2,2 ', 3,3 '-tetracarboxylic acid diphenyl sulfide dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-, 1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 2-, 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-, 1,4,5, one or more in the 8-naphthalenetetracarbacidic acidic dianhydride.
5. preparation method according to claim 1 is characterized in that, described strong polar non-proton organic solvent is N, one or more in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
6. preparation method according to claim 1 is characterized in that, the azeotropy dehydrant described in the step (2) is one or more in benzene,toluene,xylene, mono chloro benzene, the orthodichlorobenzene.
7. according to claim 1 or 6 described preparation methods, it is characterized in that the azeotropy dehydrant described in the step (2) is a toluene.
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| CN1428360A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for preparing polyimide molding powder |
| JP2005200435A (en) * | 2002-12-20 | 2005-07-28 | Kaneka Corp | Polyimide film, and metal laminated plate obtained using polyimide film |
| US20060105185A1 (en) * | 2004-11-12 | 2006-05-18 | Chang Chun Plastics Co., Ltd. | New process for preparing polyimide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1428360A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for preparing polyimide molding powder |
| JP2005200435A (en) * | 2002-12-20 | 2005-07-28 | Kaneka Corp | Polyimide film, and metal laminated plate obtained using polyimide film |
| US20060105185A1 (en) * | 2004-11-12 | 2006-05-18 | Chang Chun Plastics Co., Ltd. | New process for preparing polyimide |
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