CN1361097A - Fluorinated organic diamine and its derivatives and their prepn process and use - Google Patents
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Abstract
The present invention provides one kind of fluorinated organic diamine and its derivative and their preparation process. The present invention also provides one kind of polyimide material prepared with the fluorinated organic diamine and its preparation process.
Description
The present invention relates to a kind of fluorine-containing organic diamine and derivative thereof and their preparation method and the application aspect the synthesizing soluble polyimide material.
Fluorine-containing organic tetracarboxylic dianhydride is as 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides (6FDA) and fluorine-containing organic diamine are as 2,2 '-two (trifluoromethyl)-4,4 '-benzidines etc. usually are used to synthetic fluorine-containing polyimide (S.Sasaki, S.Nishi, Synthesis of fluorinated polyimides, in M.K.Ghosh and K.L.Mittal Ed. " Polyimides, Fundamental ﹠amp; Applications ", Marcel Dekker, Inc.1996, P71-120).The fluorinated polyimide material has excellent heat-resistant stability energy and mechanics mechanical property; low, the excellent insulation performance of specific inductivity and dielectric loss; radiation hardness, anti-α-ray, moisture resistance are wet, little, the resist chemical of water-intake rate, can be widely used in filming in the chip passivation tunic, buffering of semi-conductor, microelectronics and integrated circuit industry thereof, weld protective membrane, the interlayer dielectric of multilevel metal interconnection structure and the Liquid Crystal Molecules Alignment alignment films in the senior liquid-crystal display etc.Simultaneously, also be widely used in fields such as fire resistant resin based composites and high temperature resistant adhesivess.1993, Japanese Mitsui Toatsu ChemicalsInc. (Eur.Pat.Appl.EP 565,352) disclosed the preparation method of 4,4 '-two (3-amino-5-trifluoromethyl phenolic group) biphenyl and derivative thereof and by the material of its synthetic polyimide.People such as Havens and Hergenrother (High Performance Polymers, 1993,5 (1), 15-19) utilize 4,4 '-biphenyl or Resorcinol and 3,4,4 '-two (3-amino-5-trifluoromethyl phenolic group) biphenyl and 1 has been synthesized in the reaction of 5-dinitrobenzene trifluoromethylbenzene, two (3-amino-5-trifluoromethyl phenolic group) benzene of 4-utilize these two kinds of compounds to synthesize a series of polyimide materials with different organic aromatic series tetracarboxylic dianhydrides then.1984, Japanese Hitachi Chemical Co., Ltd (PCT Int.Appl.WO 8404,102) disclosed the technology of 4,4 '-two (4-amino-3-trifluoromethyl phenolic group) biphenyl and various organic aromatic series tetracarboxylic dianhydride synthesis of polyimides.Through C.A. and patent retrieval, a kind of fluorine-containing organic diamine and derivative thereof involved in the present invention are had no precedent relevant report, are a class novel organic compound.
The present invention discloses a kind of fluorine-containing organic diamine: 1, and two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-and derivative and their preparation method and the application aspect the synthesizing soluble polyimide material thereof.
Fluorine-containing organic diamine of the present invention and derivative thereof have the chemical structure shown in figure below:
Of the present invention 1, the preparation method of two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-and derivative thereof is undertaken by the chemical route shown in figure below: (reaction is 4-24 hour down in 100-180 ℃ under alkaline condition with 2-chloro-5-nitro-trifluoromethylbenzene and Resorcinol and derivative thereof, obtain 1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene and the derivatives thereof of 4-.This nitro-compound is obtained 1 with iron powder/HCl aqueous ethanolic solution reduction, two (4 '-amino-2-trifluoromethyl phenolic group) benzene and the derivatives thereof of 4-.
A kind of fluorine-containing organic diamine of the present invention and derivative thereof are mainly used in the preparation soluble polyimide material, and prepared polyimide has chemical structure as shown below:
R=-, O, CO, C (CF
3)
2, C (CF
3) (C
6H
5)
Polyimide material of the present invention prepares as follows:
Under nitrogen or argon shield, percentage ratio under agitation is dissolved in fluorine-containing organic diamine of the present invention and derivative thereof in the organic solvent system by weight.After treating that solid all dissolves, add molecular weight regulator and adhesion promotor.Under 0-25 ℃, add the aromatic series tetracarboxylic dianhydride in batches.Be reflected under the continuously stirring and continue 1-24 hour, obtain transparent homogeneous phase thickness polyamic acid solution.This liquid is converted into polyimide by following wherein a kind of method.1) the imidization accelerator solution is under agitation added in this solution, be warming up to 100-160 ℃ of reaction 0.5-8 hour.After being cooled to room temperature, with the liquid dispersion that obtains in organic dispersing agent.Collect settled solid,, obtain polyimide solid, powdery thing (40-200 order) 40-60 ℃ of drying then with organic alcohol solvent washing 3 times.Solid powder and organic solvent are mixed, treat that solid all dissolves after-filtration, obtains polyimide coating glue.2) liquid is coated in the surface of glass or silicon chip, progressively heating (80-350 ℃) makes polyamic acid be converted into polyimide material on baking oven or hot platform.
Can prepare the fluorine-containing organic diamine and the derivative thereof of high purity (＞99%) by preparation method of the present invention, Zhi Bei polyimide has excellent comprehensive performance as described below thus:
1) good solubility property.Dissolve in some common organic solvent, especially in low boiling point solvent, have good solubility.
2) very high heat-resisting oxidative stability.Second-order transition temperature is about 250 ℃, and heat decomposition temperature is up to 600 ℃.
3) superior mechanics mechanical property and electrical property.The elongation at break of material is between 10%-27%, and tensile strength is up to 137MPa, and modulus is 1.98GPa.The volume specific resistance of material and surface resistivity are all greater than 10
15
4) You Yi heat resistance performance.The water-intake rate of material is all less than 1%, and at 120 ℃, high-pressure water boiling is more than 120 hours under the 2atm, and the performance of material does not have considerable change.
The invention provides the following example:
Embodiment 1
47 parts of 2-chloro-5-nitro-trifluoromethylbenzenes and 11 parts of Resorcinol are dissolved in 80 parts N, in N '-N,N-DIMETHYLACETAMIDE, add 10 parts of Anhydrous potassium carbonates then.Be reflected at 130-135 ℃ of following stirring reaction 20 hours.After reactant is cooled to room temperature, filter, collect solid.Filtrate is dispersed in the water after underpressure distillation concentrates, and collects the solid of separating out.Merge the solid that obtains for twice.Be washed with water to neutrality.Drying gets 1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-.In flask at the bottom of three mouthfuls of gardens of 500ml, add 74 part 1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-, 50 parts of iron powders and 75 parts of aqueous ethanolic solutions.Slowly splashing into 8 parts of concentrated hydrochloric acids under stirring and the backflow fast, refluxed 2 hours.Add ammonia soln then, transfer to neutrality, stirred 0.5 hour.Solids removed by filtration.The filtrate distillation concentrates, and places then 10 hours.Filter, with crystal absolute ethanol washing three times, dry then.Obtain 1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-.
With 49 part 1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-under agitation add in 850 parts of N-Methyl pyrrolidone.Treat that solid all dissolves the back and adds 4 parts of two-(γ-aminopropyl) tetramethyl-silica alkane.Under 0-4 ℃, add 51 part 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides in batches.Be reflected at and carried out under 20-25 ℃ 20 hours, obtain 1000 parts of homogeneous phase thick liquids.45 parts of diacetyl oxide/pyridines (1: 1) mixture is under agitation added in the above-mentioned solution, be warming up to 40-60 ℃, reacted 3-4 hour.After being cooled to room temperature, this solution is distributed in 3000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 20 parts of dried pressed powders, add 80 parts of N-Methyl pyrrolidone or N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide solution.Adopt proper method to be coated in the position of the required protection of microelectronic device the polyimide solution that obtains, after adopting the heating of ladder-elevating temperature method to remove solvent on baking oven or the hot platform, can obtain densification, protective film that covering property is good.The device of handling through this process is difficult for bursting apart in follow-up plastic packaging process; Device heat resistance performance behind the plastic packaging is obviously improved, and at high temperature has very low leakage current and wears performance with well resisting.
Embodiment 2
With 473 parts of 2-chloro-5-nitro-trifluoromethylbenzenes and 254 parts of 2-(m-trifluoromethyl phenyl)-1, the 4-Resorcinol is dissolved in 800 parts of N, in N '-N,N-DIMETHYLACETAMIDE, adds 207 parts of Anhydrous potassium carbonates then.Be reflected at and carried out under 130-135 ℃ 14 hours.Reactant is dispersed in the water after being cooled to room temperature, collects the solid of separating out.Be washed with water to neutrality.Drying obtains 600 parts of 2-(m-trifluoromethyl phenyl)-1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-.In flask at the bottom of three mouthfuls of gardens of 1000ml, add 189 parts of 2-(m-trifluoromethyl phenyl)-1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-, 101 parts of iron powders and 150 parts of aqueous ethanolic solutions.Slowly splashing into by 8 parts of concentrated hydrochloric acids and 30 parts of solution that ethanol is made under stirring and the backflow fast, refluxed 2 hours.Add 50 parts of sodium hydroxide aqueous ethanolic solutions then, stirred 0.5 hour.Solids removed by filtration.The filtrate distillation concentrates, and places then 10 hours.Filter, with crystal absolute ethanol washing three times, dry then.Obtain 2-(m-trifluoromethyl phenyl)-1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-
With 56 parts of 2-(m-trifluoromethyl phenyl)-1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-under agitation add in 850 parts of N-Methyl pyrrolidone.Treat that solid all dissolves the back and adds 16 parts of two-(γ-aminopropyl) tetramethyl-silica alkane.Under 0-4 ℃, add 44 part 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides in batches.Be reflected at and carried out under 20-25 ℃ 20 hours, obtain 1000 parts of homogeneous phase thick liquids.45 parts of diacetyl oxide/pyridines (1: 1) mixture is under agitation added in the above-mentioned solution, be warming up to 40-60 ℃, reacted 3-4 hour.After being cooled to room temperature, this solution is distributed in 3000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 10 parts of dried pressed powders, add 90 parts of N-Methyl pyrrolidone or N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide solution.Adopt proper method to be coated in the position of semiconductor device die and required protection the gained polyimide solution, after adopting the heating of ladder-elevating temperature method to remove solvent on baking oven or the hot platform, can obtain densification, protective film that covering property is good.The device of handling through this process is difficult for bursting apart in follow-up plastic packaging process; Device heat resistance performance behind the plastic packaging is obviously improved, and at high temperature has very low leakage current and wears performance with well resisting
Embodiment 3
473 parts of 2-chloro-5-nitro-trifluoromethylbenzenes and 186 parts of Resorcinols are dissolved in 800 parts N, in N '-N,N-DIMETHYLACETAMIDE, add 300 parts of Anhydrous potassium carbonates then.Be reflected at 130-135 ℃ of following stirring reaction 18 hours.Reactant is dispersed in the water after being cooled to room temperature, collects the solid of separating out.Be washed with water to neutrality.Drying obtains 540 part 1, two (4-nitro-2-trifluoromethyl phenolic group) benzene of 3-.In flask at the bottom of three mouthfuls of gardens of 1000ml, add 170 part 1, two (4-nitro-2-trifluoromethyl phenolic group) benzene of 3-, 100 parts of iron powders and 150 parts of aqueous ethanolic solutions.Slowly splashing into 8 parts of aqueous hydrochloric acids under stirring and the backflow fast, refluxed 2 hours.Add ammoniacal liquor then, transfer solution, stirred 0.5 hour to neutral.Solids removed by filtration, the filtrate distillation concentrates, and places then 10 hours.Filter, with crystal absolute ethanol washing three times, dry then.Obtain 1, two (4-amino-2-trifluoromethyl phenolic group) benzene of 3-.
With 49 part 1, two (4-amino-2-trifluoromethyl phenolic group) benzene of 3-under agitation add in 900 parts of N-Methyl pyrrolidone.Treat that solid all dissolves the back and adds 1 part of two-(γ-aminopropyl) tetramethyl-silica alkane.Under 0-4 ℃, add 47 part 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides in batches.Be reflected at and carried out under 20-25 ℃ 20 hours, obtain the homogeneous phase thick liquid.54 parts of right-hydroxyl phenylacetic acids are added in the above-mentioned solution, under agitation be warming up to 140-160 ℃, reacted 2-3 hour.After being cooled to room temperature, this solution is distributed in 3000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 10 parts of dried pressed powders, add 90 parts of N-Methyl pyrrolidone.Treat that solid all dissolves after-filtration, obtains polyimide solution.
Embodiment 4
With 47 parts of 2-chloro-5-nitro-trifluoromethylbenzenes and 50 parts of 2-(right-trifluoromethyl)-1, the 4-Resorcinol is dissolved in 80 parts N, in N '-N,N-DIMETHYLACETAMIDE, adds 10 parts of Anhydrous potassium carbonates then.Be reflected at 130-135 ℃ of following stirring reaction 24 hours.Reactant is dispersed in the water after being cooled to room temperature, collects the solid of separating out.Be washed with water to neutrality.Drying obtains 2-(right-trifluoromethyl)-1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-.In flask at the bottom of three mouthfuls of gardens of 1000ml, add 264 parts of 2-(right-trifluoromethyl)-1, two (4 '-nitro-2-trifluoromethyl phenolic group) benzene of 4-, 100 parts of iron powders and 150 parts of aqueous ethanolic solutions.Slowly splashing into 8 parts of aqueous hydrochloric acids under stirring and the backflow fast, refluxed 2 hours.Add 50ml then and contain 50% aqueous ethanolic solution of 3.2 parts of sodium hydroxide, stirred 0.5 hour.Solids removed by filtration.The filtrate distillation concentrates, and places then 10 hours.Filter, with crystal absolute ethanol washing three times, dry then.Obtain 2-(right-trifluoromethyl)-1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-.
With 76 parts of 2-(right-trifluoromethyl)-1, two (4 '-amino-2-trifluoromethyl phenolic group) benzene of 4-under agitation add in the 897gN-methyl-2-pyrrolidone.Treat that solid all dissolves the back and adds 1 part of two-(γ-aminopropyl) tetramethyl-silica alkane.Under 0-4 ℃, add 27 part 3,3 ' 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides in batches.Be reflected at 20-25 ℃ and reacted 24 hours down, obtain the homogeneous phase thick liquid.With between 53 parts-hydroxy-benzoic acid adds in the above-mentioned solution, under agitation is warming up to 140-160 ℃, reacted 2-3 hour.After being cooled to room temperature, this solution is distributed in 3000 parts of ethanol, collects the solid separate out, and with methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 5 parts of dried pressed powders, add 95 parts of N-Methyl pyrrolidone.Treat that solid all dissolves after-filtration, obtains polyimide coating glue.
Claims (6)
1. a fluorine-containing organic diamine and derivative thereof that is expressed from the next:
Wherein Ar represents
2. method for preparing described fluorine-containing organic diamine of claim 1 and derivative thereof comprises:
With the Resorcinol or derivatives thereof shown in 2-chloro-5-nitro-trifluoromethylbenzene and the following formula
HO-Ar-OH
Under alkaline condition, reacted 4-24 hour down, obtain 1 shown in the following formula in 100-180 ℃, two (4 '-nitro-2-trifluoromethyl phenolic group) the benzene or derivatives thereofs of 4-,
Above-mentioned nitro-compound is obtained 1 with iron powder/HCl aqueous ethanolic solution reduction, two (4 '-amino-2-trifluoromethyl phenolic group) the benzene or derivatives thereofs of 4-,
Wherein, the definition of Ar is identical with the definition described in the claim 1.
3. one kind by the polyimide material shown in the following formula,
Wherein R be-, O, C=O, (CF
3)
2C, CF
3(C
6H
5) C; N is the integer of 20-70; The definition of Ar is identical with the described definition of claim 1.
4. method for preparing polyimide material according to claim 3 comprises:
(1) under nitrogen or argon shield, under agitation be dissolved in the described fluorine-containing organic diamine or derivatives thereof of claim 1 in the organic solvent;
(2) after the dissolving, under 0-25 ℃, add corresponding aroma family tetracarboxylic dianhydride;
(3) reaction is 1-24 hour, obtains transparent homogeneous phase thickness polyamic acid solution;
(4) polyamic acid solution that obtains is converted into polyimide by following wherein a kind of method: a) the imidization accelerator solution is under agitation added in this solution, be warming up to 100-160 ℃ of reaction 0.5-8 hour, perhaps b) liquid is coated in the surface of glass or silicon chip, 80-350 ℃ of heating, make polyamic acid be converted into polyimide material.
5. in accordance with the method for claim 4, wherein, the molecular weight regulator that in step (2), adds be Tetra hydro Phthalic anhydride, norbornylene acid anhydrides, maleic anhydride, aniline, right-monomethylaniline ,-monomethylaniline; Adhesion promotor is two-(γ-aminopropyl) tetramethyl-silica alkane, two-(γ-ammonia butyl) tetramethyl-silica alkane, two-(right-anilino) tetramethyl-silica alkane, two-(-anilino) tetramethyl-silica alkane, two-(γ-aminopropyl) tetraphenyl silica alkane, two-(γ-ammonia butyl) tetraphenyl silica alkane, two-(right-anilino) tetraphenyl silica alkane or two-(-anilino) tetraphenyl silica alkane.
6. in accordance with the method for claim 4, wherein, described imidization promotor is the mixture of acetic anhydride and triethylamine, the mixture of acetic anhydride and pyridine, the mixture of trifluoroacetic anhydride and pyridine, the perhaps mixture of trifluoroacetic anhydride and triethylamine.
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