CN100441652C - Method for preparing binder of polyimide of containing phenolic hydroxyl group - Google Patents
Method for preparing binder of polyimide of containing phenolic hydroxyl group Download PDFInfo
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- CN100441652C CN100441652C CNB2007100366713A CN200710036671A CN100441652C CN 100441652 C CN100441652 C CN 100441652C CN B2007100366713 A CNB2007100366713 A CN B2007100366713A CN 200710036671 A CN200710036671 A CN 200710036671A CN 100441652 C CN100441652 C CN 100441652C
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Abstract
This invention discloses a method for preparing phenolic hydroxyl-containing polyimide adhesive. The method comprises: (1) reacting phenolic hydroxyl-containing aromatic diamine, or its mixture with other aromatic diamines, with aromatic dianhydride at a mol ratio of 1:1 in strongly polar non-proton organic solvent at 0-10 deg.C for 4-8 h to obtain uniform, transparent and viscose polyhydroxyamic acid solution; (2) adding azeotropic dehydrator in nitrogen atmosphere, heating, performing imidization reaction under refluxing and dehydration at 120-160 deg.C for 1-6 h, and cooling to room temperature to obtain phenolic hydroxyl-containing polyimide adhesive. The volume ratio of azeotropic dehydrator to strongly polar non-proton organic solvent is 1 :( 1-5). The method has such advantages as easy operation, no special requirement for equipment, and high product quality. The phenolic hydroxyl-containing polyimide adhesive has such advantages as short adhesion and curing time, low energy consumption, and high adhesiveness to copper foil and polyimide thin film, and can be used to produce bi-layer flexible printed circuit boards.
Description
Technical field
The invention belongs to chemical industry polymer binder preparation method field, particularly relate to a kind of preparation method of phenolic hydroxy group polyimide adhesive.
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.
Polyimide adhesive is also used to some extent in the FPC of electronics microelectronic system, but often has phenomenons such as bonding strength is on the low side, solidification value is higher, is unfavorable for industrialization and the following process of FPC.
U.S. Pat 7026436 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and Kapton, be primarily characterized in that: aromatic series dianhydride and diamines (wherein diamines is made up of aliphatie diamine and the 10mol%～50mol% aromatic diamine of 50mol%～90mol%) obtain polyimide adhesive by condensation reaction, are used for the bonding of FPC, PCB or hard and soft printed circuit board.
The shortcoming of this method is: owing to used a large amount of aliphatic diamines, cause the thermotolerance of adhesive composition to descend greatly, its second-order transition temperature is at 150 ℃～200 ℃, thereby limited the use of printed circuit board in hot environment.
Japanese Patent JP62-278687 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and Kapton, be primarily characterized in that: the siloxanes segment is introduced in the polyimide skeleton structure, to improve the bonding strength between Copper Foil and Kapton base material.Yet its defective is also apparent: the introducing of siloxanes segment descends the second-order transition temperature of polyimide adhesive system greatly, simultaneously, the phenomenon of phase separation of adhesive composition also can occur.Therefore, be difficult to make the polyimide adhesive system of homogeneous phase transparent.
U.S. Pat 5200474 discloses a kind of preparation method of polyimide adhesive, with bonding Copper Foil and Kapton, be primarily characterized in that: bimaleimide resin and polyamic acid through malonylurea (barbituric acid) modification are formed the polyimide adhesive system.Its main drawback is: need carry out long term high temperature and solidify under 350 ℃ hot conditions.This not only expends the energy, equipment has been proposed higher technical requirements, and makes Copper Foil generation oxidizing reaction again easily.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technology is simple, solidification value is lower, set time is short, the preparation method of the high temperature resistant homogeneous phase polyimide adhesive of save energy, a kind of preparation method of phenolic hydroxy group polyimide adhesive particularly is provided, to remedy the deficiencies in the prior art or defective, satisfy the needs of scientific research and productive life.
One of technical scheme provided by the invention:
The preparation method of a kind of phenolic hydroxy group polyimide adhesive of the present invention comprises the steps:
(1) mol ratio is that the mixture of 1: 1 phenolic hydroxy group aromatic dicarboxylic amine compound or itself and other aromatic diamine and aromatic dicarboxylic acid anhydride are in strong polar non-proton organic solvent, obtain homogeneous phase, transparent, heavy-gravity polyhydroxyamide acid solution in reaction under 0 ℃～10 ℃ after 4～8 hours.
(2) in the nitrogen atmosphere, add azeotropy dehydrant, heating, 120 ℃～160 ℃ of backflow azeotropic dehydrations imidization 1～6 hour, be cooled to room temperature, obtained the phenolic hydroxy group polyimide adhesive, wherein azeotropy dehydrant is 1: 1～5 with the volume ratio of strong polar non-proton organic solvent.
Optimal technical scheme provided by the invention:
Described phenolic hydroxy group aromatic dicarboxylic amine compound is 4,4 '-diamino-4 "-hydroxyl tritane (DAHTM); 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 aromatic diamine is 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 (BAPOPP) of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane (3BAPOPP) of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (4BAPOFP) of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa (3BAPOFP) of 2-, 2, two (4-aminophenyl) HFC-236fa (BAPHFP) of 2-, 2, two (4-amino-benzene oxygen) cyanobenzenes (26B4APBN) of 6-, 2, one or more in two (3-amino-benzene oxygen) cyanobenzenes (26B3APBN) of 6-.
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, one or more in the 8-naphthalenetetracarbacidic acidic dianhydride (NTDA).
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;
-D-：
The invention has the beneficial effects as follows: (1) the present invention is the commercial run of preparation phenolic hydroxy group polyimide adhesive; (2) reduced the solidification value of polyimide adhesive, also reduced set time simultaneously.This not only can make FPC user save energy consumption and man-hour, and can save the cost of investment of equipment; (3) simple to operate, equipment there is not particular requirement, less investment can be finished the operating process of preparation phenolic hydroxy group polyimide adhesive in same reactor; (4) polyimide adhesive system homogeneous phase transparent does not have phenomenon of phase separation after Kapton and the Copper Foil adhering and solidifying; (5), polyimide adhesive is improved to the bonding strength of Kapton and Copper Foil, and helps improving the resistance of oxidation of Copper Foil because of the existence of phenolic hydroxyl group in the molecular structure.
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.
Embodiment 1
With 3.66 gram (0.01 moles) 2, two (the 3-amino-4-hydroxy phenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa (B3A4HPFP), 2.26 gram (0.01 mole) 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane (DMMDA) and 5.85 gram (0.02 moles) 1, two (4-amino-benzene oxygen) benzene (134BAPB) of 3-join and have water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 100 gram N,N-dimethylacetamide (DMAc) subsequently, stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, adds 6.20 gram (0.02 moles) 3 in batches, 3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA) and 6.44 gram (0.02 moles) 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA) after 4 hours, obtains thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 20 gram toluene, heat temperature raising to 120 ℃, reflux water-dividing was closed heating system after 2 hours, stirred, and naturally cooled to room temperature, had obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.26N/mm.
Embodiment 2
With 2.90 gram (0.01 moles) 4,4 '-diamino-4 "-hydroxyl tritane (DAHTM); 2.00 gram (0.01 moles) 3; 4 '-diaminodiphenyl oxide (34ODA); 5.18 gram (0.01 moles) 2; two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (4BAPOFP) of 2-; 2.92 gram (0.01 moles) 1, two (4-amino-benzene oxygen) benzene (134BAPB) of 3-join and have water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 100 gram N-N-methyl-2-2-pyrrolidone N-s (NMP) subsequently, stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, add 5.20 gram (0.01 mole) bisphenol A-type two ether dianhydrides (BPADA) in batches, 6.44 gram (0.02 mole) 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA) and 2.49 gram (0.01 mole) biphenyl dianhydrides (BPDA), after 8 hours, obtain thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 60 gram dimethylbenzene, heat temperature raising to 140 ℃, reflux water-dividing be after 1 hour,, close heating system, stir, naturally cool to room temperature, obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.24N/mm.
Embodiment 3
With 3.66 gram (0.01 moles) 2, two (the 3-amino-4-hydroxy phenyl)-1 of 2-, 1,1,3,3,3-HFC-236fa (B3A4HPFP), 4.10 gram (0.01 mole) 2, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP) of 2-, 2.00 gram (0.01 mole) 3,4 '-diaminodiphenyl oxide (34ODA) and 2.00 gram (0.01 moles) 4,4 '-diaminodiphenyl oxide (44ODA) joins and has water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 120 gram N subsequently, dinethylformamide (DMF), stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, adds 9.30 gram (0.03 moles) 3 in batches, 3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA) and 3.22 gram (0.01 moles) 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA) after 6 hours, obtains thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 20 gram toluene, heat temperature raising, reflux water-dividing be after 2 hours,, close heating system, stir, naturally cool to room temperature, obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.12N/mm.
Embodiment 4
With 2.58 gram (0.01 moles) 2, two (the 3-amino-4-hydroxy phenyl) propane (B3A4HPP) of 2-, 5.18 gram (0.01 mole) 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-((4BAPOFP) and 4.00 gram (0.02 moles) 3,4 '-diaminodiphenyl oxide (34ODA) joins and has water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 80 gram N-N-methyl-2-2-pyrrolidone N-s (NMP) subsequently, stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, add 3.10 gram (0.01 moles) 3 in batches, 3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA), 3.22 gram (0.01 mole) 3,3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA), 5.20 gram (0.01 mole) bisphenol A-type two ether dianhydrides (BPADA) and 2.49 gram (0.01 mole) biphenyl dianhydrides (BPDA), after 8 hours, obtain thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 20 gram toluene, heat temperature raising, reflux water-dividing was closed heating system after 6 hours, stirred, and naturally cooled to room temperature, had obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.27N/mm.
Embodiment 5
With 2.90 gram (0.01 moles) 4,4 '-diamino-4 "-hydroxyl tritane (DAHTM); 3.66 gram (0.01 moles) 2; two (the 3-amino-4-hydroxy phenyl)-1 of 2-; 1; 1; 3,3,3-HFC-236fa (B3A4HPFP), 3.17 gram (0.01 mole) 2, two (4-amino-benzene oxygen) cyanobenzenes (26B4APBN) of 6-and 5.18 gram (0.01 moles) 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (4BAPOFP) of 2-join and have water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 120 gram N subsequently, N-N,N-DIMETHYLACETAMIDE (DMAc), stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, add 12.88 gram (0.04 moles) 3 in batches, 3 ', 4,4 '-tetracarboxylic acid benzophenone dianhydride (BTDA), after 4 hours, obtain thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 40 gram dimethylbenzene, heat temperature raising, reflux water-dividing was closed heating system after 1 hour, stirred, and naturally cooled to room temperature, had obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.30N/mm.
Embodiment 6
With 2.90 gram (0.01 moles) 4,4 '-diamino 4 "-hydroxyl tritane (DAHTM); 2.00 gram (0.01 moles) 3; 4 '-diaminodiphenyl oxide (34ODA); 5.18 gram (0.01 moles) 2; two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (4BAPOFP) of 2-and 2.92 gram (0.01 moles) 1; two (4-amino-benzene oxygen) benzene (134BAPB) of 3-join and have water-and-oil separator, reflux condensing tube, thermometer, in the reaction flask of logical nitrogen tube and electric mixer, add 140 gram N subsequently, N-N,N-DIMETHYLACETAMIDE (DMAc), stir under the room temperature, after making it to dissolve fully, ice-water bath is cooled to below 5 ℃, add 10.40 gram (0.02 mole) bisphenol A-type two ether dianhydrides (BPADA) and 6.20 gram (0.02 moles) 3 in batches, 3 ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride (ODPA) after 8 hours, obtains thick polyhydroxyamide acid solution in 0 ℃～10 ℃ following stirring reactions.Subsequently, feed nitrogen, add 40 gram toluene, heat temperature raising, reflux water-dividing was closed heating system after 1 hour, stirred, and naturally cooled to room temperature, had obtained thickness, homogeneous phase, transparent phenolic hydroxy group polyimide adhesive.
Thickness, homogeneous phase, the transparent phenolic hydroxy group polyimide adhesive of above-mentioned gained evenly is coated on after on the Kapton base material that surface corona is handled, with the compound hot pressing moulding of Copper Foil, curing process is: room temperature → 100 ℃/0.5h+150 ℃/0.5h+200 ℃/0.5h+240 ℃/0.5h.
The stripping strength of gained Kapton base material and Copper Foil is 1.36N/mm.
Claims (6)
1, a kind of preparation method of phenolic hydroxy group polyimide adhesive, 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 itself and other aromatic diamine and aromatic dicarboxylic acid anhydride are in strong polar non-proton organic solvent, obtain homogeneous phase, transparent, heavy-gravity polyhydroxyamide acid solution in reaction under 0 ℃～10 ℃ after 4～8 hours.
(2) in the nitrogen atmosphere, add azeotropy dehydrant, heating, 120 ℃～160 ℃ of backflow azeotropic dehydrations imidization 1～6 hour, be cooled to room temperature, obtained the phenolic hydroxy group polyimide adhesive, wherein azeotropy dehydrant is 1: 1～5 with the volume ratio of strong polar non-proton organic solvent.
2, a kind of phenolic hydroxy group polyimide adhesive preparation method according to claim 1, it is characterized in that described phenolic hydroxy group aromatic dicarboxylic amine compound is 4,4 '-diamino-4 "-the hydroxyl tritane; 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 the described a kind of phenolic hydroxy group polyimide adhesive of claim 1, it is characterized in that, described other aromatic diamine is a 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, two (4-aminophenyl) HFC-236fa of 2-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, one or more in two (3-amino-benzene oxygen) cyanobenzenes of 6-.
4, a kind of phenolic hydroxy group polyimide adhesive 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, a kind of phenolic hydroxy group polyimide adhesive preparation method according to claim 1, it 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, a kind of phenolic hydroxy group polyimide adhesive 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.
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