CN1229421C - Soluble fluorine-containing polyamidoimide resin, its preparation method and application - Google Patents

Soluble fluorine-containing polyamidoimide resin, its preparation method and application Download PDF

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CN1229421C
CN1229421C CN 03109354 CN03109354A CN1229421C CN 1229421 C CN1229421 C CN 1229421C CN 03109354 CN03109354 CN 03109354 CN 03109354 A CN03109354 A CN 03109354A CN 1229421 C CN1229421 C CN 1229421C
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fluorine
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trifluoromethyl
imide resin
benzene
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CN1535994A (en
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杨士勇
李仲晓
范琳
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Institute of Chemistry CAS
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Abstract

The present invention relates to a soluble fluorine-containing polyamide imide resin which can dissolve in acetone and tetrahydrofuran. 8 to 12 shares of fluorine-containing aromatic diacid and aromatic diamine monomer dissolve in 30 to 50 shares of non-proton polar solvent. 5 to 10 shares of pyridine, 5 to 15 shares of triphenyl phosphite and 2 to 8 shares of inorganic salt are added in the non-proton polar solvent. The reaction is carried out at the temperature of 100 to 130 DEG C for 3 to 6 hours to obtain a yellowish viscous solution. The yellowish viscous solution is deposited, washed and dried to obtain a hoary or yellowish polyamide imide resin which can be made into a pliable film. Coating the resin solution on the surface of a semiconductor chip has the functions of chip protection, leakage current reduction, moisture protection, stress absorption, etc.

Description

A kind of soluble fluorine-containing polyamide-imide resin and its production and use
Technical field:
The present invention relates to a kind of soluble fluorine-containing polyamide-imide resin and its production and use.
Technical background:
Polyamidoimide is a class contains acid amides functional group and imide functional group simultaneously in the main polymer chain structure a multipolymer, the premium properties that has aromatic polyimide and aromatic polyamide concurrently has many advantages such as high temperature resistant, low temperature resistant, corrosion-resistant, high insulation, low-dielectric loss, mechanical property excellence in one.Compare with polyimide, polyamidoimide can obviously improve solubility property and processing characteristics on the basis that keeps the excellent heat resistance energy.Therefore, can be used as the heat resistant structure material, high temperature insulation solvent impregnated resin, high temperature resistant binder resin etc. are applied to many high-technology fields such as aerospace, power electronics.
The main drawback of polyamidoimide is water-intake rate higher (4-6%), and anti-hydrolytic performance, electrical insulation capability and dielectric properties remain further to improve and improve.It is generally acknowledged that the less fragrant ehter bond of polarity of introducing nonpolar aliphatics substituted radical or certain-length in the main polymer chain skeleton of polyamidoimide can effectively improve solvability, and reduces its water-intake rate.People such as Yang (Yang, C.P.; Chen, R.S.; Chen, C.D.JPolym Sci, Part A:Polym Chem, 2001,39,775-787.) reported a kind of novel polyamide imide polymer with volution backbone structure, its constructional feature is to have a large amount of nonpolar side-draws for group and irregular backbone structure.Its water-intake rate is starkly lower than similar polyamidoimide material between 1.42-3.05%.People [Mesaki, M. such as Masakazu Mesaki; Goda H.Electrical Insulation Conferenceand Electrical Manufacturing ﹠amp; Coil Winding Conference, P1-4, Oct.16-18,2001, Ohio, US] report, the in-situ hybridization material that is formed by polyamidoimide and silicon-dioxide has lower water-intake rate; Its water-intake rate is relevant with the content of silicon-dioxide; When dioxide-containing silica was 2%, water-intake rate was minimum, be 2.4% (95%RH, 24h[%]), reduce about 55% than pure polyamidoimide.Find that simultaneously the specific inductivity of material and the content of silicon-dioxide also have relation; With the raising of dioxide-containing silica, specific inductivity slightly reduces., the shortcoming of this method is that the stability in storage of polymkeric substance/nano-mixture is relatively poor.
Fluoro-containing group is introduced the water-intake rate that can effectively reduce polyamidoimide in the polymkeric substance, can reduce the specific inductivity and the visible light transmissivity of material simultaneously.Hamciuc[Hamciuc, C.; Ion, Sava; Ilie, Diaconu; Bruma, M.High Perform Polym 2000,12,265] and people [Yang, C.P. such as Yang; Chen, R.S.; Wang, M.J.J Polym Sci, Part A:Polym Chem, 2001,39,775] reported a kind of based on 4, the fluorine-containing polyamidoimide polymer materials of 4-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides (6FDA).The introducing of fluoro-containing group can make the water-intake rate of material reduce to below 2%, and solubility property is significantly improved simultaneously.
Summary of the invention:
The present invention discloses a kind of polyamide-imide resin that is passed through the condensation polymerization prepared in reaction by fluorinated aromatic diacid and aromatic diamine.Advantages such as described polyamide-imide resin has good heat stability, mechanics good mechanical property, visible transparent rate height, and water-intake rate is low; Not only dissolve in strong polar aprotic organic solvent, and in common organic solvent, also have the good solubility energy.
Fluorine-containing polyamidoimide of the present invention has following typical chemical structure:
Figure C0310935400051
R wherein 1For:
Figure C0310935400052
R wherein 2For:
Figure C0310935400053
N=8～100 wherein.
The preparation of polyamide-imide resin of the present invention is undertaken by following sequential steps:
Under nitrogen or argon shield, 8～12 parts of aromatic diamines are dissolved in 30-50 part polar aprotic solvent; Then 8～12 parts of fluorine-containing organic diacid gradation are added; Add catalyzer (comprising 5～15 portions of triphenyl phosphites, 5～10 parts of pyridines and 2～8 parts of inorganic salt) subsequently.Polyreaction through 3～6 hours under rare gas element (comprising nitrogen, argon gas) protection generates polyamidoimide solution.After precipitation in methyl alcohol, separation, washing, drying, obtain the polyamidoimide solid resin.This solid resin is dissolved in the suitable organic solvent system forms polymers soln; Then it is adopted methods such as the method for being coated with of getting rid of, pickling process, spraying method or silk screen printing to be coated on the substrate, add the heat extraction solvent after, obtain flexible polymeric film, its typical performance is as shown in table 1.
Fluorinated aromatic diacid of the present invention is 1,4-(2-trifluoromethyl-4-amino-benzene oxygen) benzene-trimellitic acid 1,2-anhydride imines diacid PBTB, 1,3-(2-trifluoromethyl-4-amino-benzene oxygen) benzene-trimellitic acid 1,2-anhydride imines diacid MBTB or 1-trifluoromethyl-3, the mixture of 5-diaminobenzene-trimellitic acid 1,2-anhydride imines diacid TFTB or above three kinds of acid.
Fluorinated aromatic diamines of the present invention is 1, two (the 4-amino-3 of 1-, the 5-3,5-dimethylphenyl)-(3-trifluoromethyl) methane TFPM, 4-(3-trifluoromethyl)-2, two (3-aminophenyl) the pyridine TBAP of 6-, 1, two (4-the aminophenyl)-1-(3-trifluoromethyl)-2 of 1-, 2,2-Halothane BTFE, 1, two (4-amino-3-4-trifluoromethylphenopendant) the benzene m-BTPB of 3-, 1, two (4-amino-3-4-trifluoromethylphenopendant) the benzene p-BTPB or 1 of 4-, two (4-the aminophenyl)-1-(3, the 5-trifluoromethyl)-2 of 1-, 2, the mixture that 2-Halothane 9FDAM or above-claimed cpd mix by arbitrary proportion.
The organic aprotic solvent of polarity of the present invention is N-Methyl pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide or dimethyl sulfoxide (DMSO) or the mixed solvent that is mixed with arbitrary proportion by above-mentioned solvent.
The performance of the fluorine-containing polyamidoimide film of table 1
Embodiment Organic diacid Organic diamine Limiting viscosity (dL/g) Second-order transition temperature (℃) a Decomposition temperature (℃) b Membrane quality
4 P-BTTB p-BTPB 0.67 264 607 Gentle and tough
5 P-BBTB TBAP 0.56 266 584 Gentle and tough
6 P-BBTB BTFE 0.61 257 567 Gentle and tough
7 P-BBTB TFPM 1.10 260 549 Gentle and tough
8 P-BBTB 9FDAM 0.64 251 515 Gentle and tough
9 m-BTTB 9FDAM 0.58 249 504 Gentle and tough
10 TFTB 9FDAM 0.67 288 514 Gentle and tough
A. measure by differential thermal analysis (DSC); B. under nitrogen, measure.
Polyamide-imide resin of the present invention, its limiting viscosity is between 0.40-1.8dL/g.This resin solution has extended storage stability, places three months no demixing phenomenons, and viscosity does not have considerable change.Solution has good flowability and levelling property, can evenly apply on sheet glass, and after solvent is removed in 60-200 ℃ stage intensification thermal treatment, form tough polymeric film.The gained film has good resistance to elevated temperatures, and second-order transition temperature (Tg) is between 200-350 ℃, and the decomposition temperature under the nitrogen (Td) is greater than 500 ℃.The performance of typical polyamides imide membrane is as shown in table 1.
Polyamidoimide film of the present invention has good mechanical property, electrical property and low water absorption (table 2).Such material has good visible transparent, and is of light color, the film of 30 μ m to the transmitance of 450nm light greater than 80%.
Mechanical property, electrical property and the water-intake rate of the fluorine-containing polyamidoimide film of table 2
T S (MPa) E B (％) Y M (GPa) R S×10 14 (Ω) R V×10 15 (Ω·cm) Tanδ ×10 -3 Specific inductivity (1MHz) Water-intake rate (%)
4 88.5 17 2.85 1.1 1.9 3.03 3.34 0.72
5 96.7 17 3.02 3.1 2.9 5.05 3.52 0.76
6 84.5 16 2.79 8.2 9.2 3.84 3.26 0.63
7 90.2 18 2.37 2.2 6.4 4.85 3.38 0.89
8 82.9 17 2.03 8.4 6.9 3.25 3.94 0.59
9 72.9 18 1.58 6.7 5.1 3.29 4.17 0.62
10 81.7 17 1.84 7.3 5.8 3.28 4.03 0.68
Polyamide-imide resin of the present invention has excellent comprehensive performances in organic solvent, can be applicable to aspects such as the interlayer dielectric/insulating layer film of surperficial chip passivation layer, stress buffer undercoat, contact protective membrane, multilayer interconnection circuit in the microelectronics Packaging and welded ball array encapsulation, wafer-level package.
Embodiment:
Example 1 adds 100 part 1 in a 1000ml there-necked flask that is equipped with mechanical stirring, water condensing tube and nitrogen inlet, two (4-amino-3-4-trifluoromethylphenopendant) the benzene m-BTPB of 3-, 200 parts of trimellitic acid 1,2-anhydrides and 700 parts of N-Methyl pyrrolidone NMP.Stirring at room 12 hours adds 600 parts of toluene and 5 parts of isoquinoline 99.9 then.Water trap is installed, reflux, methylbenzene azeotropic dewatered 10 hours.System temperature rises to 180 ℃ then, removes remaining toluene as far as possible.Be chilled to room temperature, be poured in 3000 parts of methyl alcohol, separate out precipitation.Suction filtration is used methyl alcohol and hot wash successively, and is dry then.Use N, dinethylformamide DMAc recrystallization obtains 232g white powdery fluorinated aromatic diacid, and 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3--trimellitic acid 1,2-anhydride imines diacid m-PBTB (83%).Fusing point: 286-287 ℃ (DSC). 1HNMR (DMSO-d 6δ, ppm): 8.39-8.43 (d, 2H), 8.27 (s, 2H), 7.92-7.98 (d, 2H), 7.95 (s, 2H), 7.77-7.80 (d, 2H), 7.54-7.59 (t, 1H), 7.36-7.39 (d, 2H), and 7.03-7.06 (d, 2H), 6.72 (s, 1H) .FT-IR (KBr, cm -1): 3426,3091,1782,1726,1662,1616,1501,1437,1243,1135. ultimate analysis (C 38H 18F 6N 2O 10): C, 58.77%; H, 2.34%; N, 3.61%. actual measurement: C, 58.53%; H, 2.51%; N, 3.49%.
Example 2 adds 100 part 1 in a 1000ml there-necked flask that is equipped with mechanical stirring, water condensing tube and nitrogen inlet, two (4-amino-benzene oxygen)-2-(3-trifluoromethyl) the benzene m-BTPB of 4-, 200 parts of trimellitic acid 1,2-anhydrides and 600 parts of NMP.Stirring at room 12 hours adds 600 parts of toluene and 5 parts of isoquinoline 99.9 then.Water trap is installed, reflux, methylbenzene azeotropic band water 10 hours.System temperature rises to 180 ℃ then, removes residual toluene as far as possible.Be chilled to room temperature, be poured in 3000 parts of methyl alcohol, separate out precipitation.Suction filtration is used methyl alcohol and hot water cleaning down successively, press dry.Use N, the dinethylformamide recrystallization obtains 230g white meal, and 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4--trimellitic acid 1,2-anhydride imines diacid p-PBTB (productive rate: 87%).M.p.330 ℃ (DSC). 1H NMR (DMSO-d 6, δ ppm): 8.39-8.43 (d, 2H), 8.31 (s, 2H), 8.05-8.08 (d, 2H), 7.94 (s, 2H), 7.72-7.77 (d, 2H), 7.28 (s, 4H), 7.22-7.26 (d, 2H) .FT-IR (KBr, cm -1): 3497,3086,1785,1730,1600,1492,1438,1244,1124. ultimate analysis (C 38H 18F 6N 2O 10): C, 58.77%; H, 2.34%; N, 3.61%. actual measurement: C, 58.49%; H, 2.46%; N, 3.52%.
Example 3 adds 50 part 3,5-two (trifluoromethyl) aniline, 100 parts of trimellitic acid 1,2-anhydrides and 600 parts of NMP in a 1000ml there-necked flask that is equipped with mechanical stirring, water condensing tube and nitrogen inlet.Stirring at room 12 hours adds 600 parts of toluene and 6 parts of isoquinoline 99.9 then.Water trap is installed, reflux, toluene band water 10 hours.System temperature rises to 180 ℃ and removes residual toluene as far as possible.Be chilled to room temperature, be poured in 2000 parts of methyl alcohol.Suction filtration is successively with methyl alcohol and hot water cleaning down and press dry.Use N, the dinethylformamide recrystallization obtains 133g white meal, 1-trifluoromethyl-3,5-diaminobenzene-trimellitic acid 1,2-anhydride imines diacid TFTB (productive rate: 84%).M.p.330 ℃ (DSC). 1H NMR (DMSO-d 6, δ ppm): 8.42-8.44 (d, 2H), 8.33 (s, 2H), 8.10-8.15 (d, 2H), 8.03 (s, 2H), 7.98 (s, 2H) .FT-IR (KBr, cm -1): 3497,3086,1785,1730,1600,1492,1438,1244,1124. ultimate analysis (C 25H 11F 3N 2O 8): C, 57.26%; H, 2.11%; N, 5.34%. actual measurement: C, 56.98%; H, 2.23%; N, 5.19%.
Example 4 adds 8 parts of p-BTTB in there-necked flask at the bottom of the 500ml garden, 8 parts of BTPB, 2 parts of lithium chlorides, 30 parts of NMP, 5 parts of pyridines and 5 portions of triphenyl phosphites, under nitrogen gas stream in 100 ℃ of heated and stirred 3 hours.Be chilled to 25 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain light yellow thread precipitation.Wash repeatedly with methyl alcohol and hot water successively then, 100 ℃ of vacuum-dryings obtain 58g polyamidoimide (94%).Ultimate analysis (C 29H 14F 6N 2O 5): C, 59.59%; H, 2.40%; N, 4.80%; Actual measurement: C, 58.85%; H, 2.48%; N, 4.47%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours;
Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to room temperature, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 5 adds 12 parts of p-BTTB in the there-necked flask of 1000ml, 12 parts of TBAP, and 8 parts of inorganic salt, 50 parts NMP, 10 parts of pyridines and 15 portions of triphenyl phosphites, heated and stirred is 6 hours under nitrogen gas stream.Be chilled to 30 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain yellow thread precipitation.Wash repeatedly with methyl alcohol and hot water successively then.100 ℃ of vacuum-dryings obtain the 56g polymkeric substance.Productive rate: 95%.Ultimate analysis (C 62H 32F 9N 5O 8): C, 65.04%; H, 2.80%; N, 6.12%; Actual measurement: C, 64.95%; H, 2.86%; N, 5.91%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to room temperature, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 6 adds 10 parts p-BTTB in the there-necked flask of 1000ml, 10 parts of BTFE, and 6 parts of inorganic salt, 50 parts of NMP, 8 parts of pyridines and 12 portions of triphenyl phosphites, heated and stirred is 4 hours under nitrogen gas stream.Be chilled to 25 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain the thread precipitation of canescence.Wash repeatedly with methyl alcohol and hot water successively then.100 ℃ of vacuum-dryings get 56g polymkeric substance (93%).Ultimate analysis (C 59H 30F 12N 4O 8): C, 61.63%; H, 2.61%; N, 4.87%; Actual measurement: C, 61.10%; H, 2.93%; N, 4.80%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to room temperature, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 7 adds 10 parts p-BTTB in the there-necked flask of 1000ml, 10 parts of TFPM, and 6 parts inorganic salt, 50 parts NMP, 8 parts pyridine and 12 portions of triphenyl phosphites, heated and stirred is 3 hours under nitrogen gas stream.Be chilled to 30 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain the thread precipitation of canescence.Wash repeatedly with methyl alcohol and hot water successively then.100 ℃ of vacuum-dryings get 57g polymkeric substance (95%).Ultimate analysis (C 62H 39F 9N 4O 8): C, 64.53%; H, 3.38%; N, 4.86%; Actual measurement: C, 64.16%; H, 3.47%; N, 4.77%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to room temperature, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 8 adds 10 parts p-BTTB in the there-necked flask of 1000ml, 10 parts 9FDAM, and 5 parts inorganic salt, 50 parts NMP, 6 parts of pyridines and 12 portions of triphenyl phosphites, heated and stirred is 3 hours under nitrogen gas stream.Be chilled to 25 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain the thread precipitation of canescence.Wash repeatedly with methyl alcohol and hot water successively then, 100 ℃ of vacuum-dryings get 60g polymer product (93%).Ultimate analysis (C 60H 29F 15N 4O 8): C, 59.12%; H, 2.40%; N, 4.60%; Actual measurement: C, 58.74%; H, 2.53%; N, 4.39%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; Be cooled to 25 ℃, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 9 adds 10 parts m-BTTB in the there-necked flask of 1000ml, 10 parts 9FDAM, and 7 parts inorganic salt, 50 parts NMP, 6 parts of pyridines and 12 portions of triphenyl phosphites, heated and stirred is 5 hours under nitrogen gas stream.Be chilled to 25 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain the thread precipitation of canescence.Wash repeatedly with methyl alcohol and hot water successively then, 100 ℃ of vacuum-dryings get 60.1g polymkeric substance (93%).Ultimate analysis (C 60H 29F 15N 4O 8): C, 59.12%; H, 2.40%; N, 4.60%; Found:C, 58.95%; H, 2.61%; N, 4.42%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to 25 ℃, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.
Example 10 adds 10 parts TFTB in the there-necked flask of 1000ml, 10 parts of 9FDAM, and 6 parts inorganic salt, 50 parts NMP, the triphenyl phosphite of 60 parts pyridine and 12 parts, heated and stirred is 4 hours under nitrogen gas stream.Be chilled to 25 ℃, under constantly stirring, the heavy-gravity reaction solution slowly be poured in 300 parts of methyl alcohol, obtain light yellow thread precipitation.Wash repeatedly with methyl alcohol and hot water successively then, 100 ℃ of vacuum-dryings get 48.8g polymer product (96%).Ultimate analysis (C 47H 22F 12N 4O 6): C, 59.12%; H, 2.40%; N, 4.60%; Found:C, 58.74%; H, 2.53%; N, 4.39%.
20 parts of above-mentioned polyamidoimides and 80 parts of NMP are mixed, stir the polymers soln that obtains homogeneous phase transparent after 6 hours; Polymers soln is coated on the sheet glass, and then in 100 ℃ of heating 1 hour, 150 ℃ kept 1 hour down, and 200 ℃ kept 3 hours; After being cooled to 25 ℃, polymeric film is peeled off from sheet glass.
Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 3 hours, and 275～300 ℃ kept 1 hour; Then, the plastic packaging circuit that obtains behind plastic packaging has the protection chip, reduces effects such as leakage current, protection against the tide, absorption stress.

Claims (6)

1. soluble fluorine-containing polyamide-imide resin is characterized in that described fluorine-containing polyamide-imide resin has following chemical structure:
R wherein 1:
Figure C031093540002C2
R wherein 2:
Figure C031093540002C3
Wherein: n=8～100;
This fluorine-containing polyamide-imide resin, dissolve in acetone, butanone, pimelinketone, tetrahydrofuran (THF), ethylene glycol monoemethyl ether, glycol dimethyl ether, m-methyl phenol, butyl glycol ether, butyl glycol ether acetic ester, ethyl cellosolve acetate, gamma-butyrolactone, N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, the mixture of N '-dimethyl formamide or dimethyl sulfoxide (DMSO) or these solvents.
2. according to the preparation method of the described a kind of fluorine-containing polyamide-imide resin of claim 1, it is characterized in that step is carried out in the following order: (1) is under nitrogen or argon shield, 8～12 parts of organic aromatic diacid and organic aromatic diamine monomer are dissolved in 30-50 part aprotic polar solvent, add 5-10 part pyridine, 5-15 part triphenyl phosphite, 2-8 part inorganic salt, reacted 3～6 hours down at 100-130 ℃, obtain lurid viscous solution; (2) with in the above-mentioned solution impouring methyl alcohol, separate out the resin precipitated thing, after washing drying, obtain canescence or lurid polyamide-imide resin;
Described organic aromatic diacid is 1,4-(2-trifluoromethyl-4-amino-benzene oxygen) benzene-trimellitic acid 1,2-anhydride imines diacid, 1,3-(2-trifluoromethyl-4-amino-benzene oxygen) benzene-trimellitic acid 1,2-anhydride imines diacid or 1-trifluoromethyl-3,5-diaminobenzene-trimellitic acid 1,2-anhydride imines diacid or above two or more sour mixtures;
Described organic aromatic diamine is 1,1-(4-amino-3, the 5-dimethyl benzene)-(3-trifluoromethylbenzene) methane, 4-(3-trifluoromethyl)-2, two (3-aminophenyl) pyridines of 6-, 1, two (4-the aminophenyl)-1-(3-trifluoromethyl)-2 of 1-, 2, the 2-Halothane, 1, two (4-amino-benzene oxygen)-2-(3-trifluoromethyl) benzene of 3-, 1, two (4-amino-benzene oxygen)-2-(3-trifluoromethyl) benzene or 1 of 4-, two (4-the aminophenyl)-1-(3, the 5-trifluoromethyl)-2 of 1-, 2, the mixture of 2-Halothane or above two or more amine.
3. the preparation method of a kind of fluorine-containing polyamide-imide resin according to claim 2, it is characterized in that described aprotic polar solvent is N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide or the mixed solvent that mixes by a certain percentage.
4. the preparation method of a kind of fluorine-containing polyamide-imide resin according to claim 2 is characterized in that employed inorganic salt comprise calcium chloride, lithium chloride or its mixture.
5. the purposes of a kind of fluorine-containing polyamide-imide resin according to claim 1 is characterized in that this resin can be made into flexible fluorine-containing polyamidoimide film.
6. the purposes of a kind of fluorine-containing polyamide-imide resin according to claim 7 is characterized in that adopting and gets rid of the method for being coated with, pickling process, spraying method or method for printing screen and be coated on the substrate, makes after heating desolventizes.
CN 03109354 2003-04-04 2003-04-04 Soluble fluorine-containing polyamidoimide resin, its preparation method and application Expired - Fee Related CN1229421C (en)

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CN100462403C (en) * 2006-07-24 2009-02-18 海洋化工研究院 Blend of polyimide polymer and its use as high temperature resisting dipping glue
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KR101870341B1 (en) * 2013-12-26 2018-06-22 코오롱인더스트리 주식회사 Colorless Polyamide―imide Resin and Film Thereof
CN110258118B (en) * 2019-07-12 2021-07-13 开封大学 Water-soluble temperature-resistant carbon fiber sizing agent and preparation method thereof
CN112812301A (en) * 2021-01-04 2021-05-18 株洲时代新材料科技股份有限公司 Preparation of soluble polyimide, black soluble polyimide composite glue solution prepared from soluble polyimide, preparation and application of black soluble polyimide composite glue solution

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