CN100400529C - Fluoro-aromatic organic tetracarboxylic dianhydride and its preparation method and use - Google Patents
Fluoro-aromatic organic tetracarboxylic dianhydride and its preparation method and use Download PDFInfo
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Abstract
The present invention relates to a preparation method of fluorine-containing aromatic organic tetracid etrahydric dianhydride and a derivative and a use thereof. Substituted alpha, alpha, alpha-trifluoromethyl acetophenone is prepared from metal trifluoroacetate and substituted halogeno benzene by Grignard reaction; a fluorine-containing aromatic tetramethyl compound is prepared from the substituted alpha, alpha, alpha-trifluoromethyl acetophenone and o-xylene by condensation reaction under the action of strong acid; fluorine-containing aromatic organic tetracid is prepared from the fluorine-containing aromatic tetramethyl compound by high-temperature nitric acid oxidation or KMnO4 oxidation; the fluorine-containing aromatic organic tetracid etrahydric dianhydride and the derivative thereof are prepared from the fluorine-containing aromatic organic tetracid by reflux or heating molten dehydration in acetic anhydride/acetic acid. After polyamic acid is prepared from the fluorine-containing aromatic organic tetracid etrahydric dianhydride, the derivative thereof and aromatic organic diamine by polycondensation reaction in polar solvent and treated by chemical imidization or heat imidization, fluorine-containing aromatic polyimide is acquired. The polymer has excellent comprehensive performance.
Description
Technical field
The present invention relates to organic tetracarboxylic dianhydride of a kind of fluorinated aromatic and derivative thereof.
The invention still further relates to the preparation method of organic tetracarboxylic dianhydride of above-mentioned fluorinated aromatic and derivative thereof.
The invention still further relates to the purposes of organic tetracarboxylic dianhydride of above-mentioned fluorinated aromatic and derivative thereof.
Background technology
Polyimide material has the excellent comprehensive performance, has broad application background and huge commercial value at aspects such as space flight, aviation, space, microelectronics, electric apparatus.The organic tetracarboxylic dianhydride of aromatic series is the important source material of preparation polyimide material, has very big influence for the performance of polyimide material.The organic tetracarboxylic dianhydride of aromatic series commonly used at present mainly comprises 1,2,4,5-pyromellitic acid dianhydride (PMDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-BPDA (BPDA), 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 4,4 '-(hexafluoro sec.-propyl) two O-phthalic acid dianhydrides (6FDA) etc.; Because the kind of aromatic series tetracarboxylic dianhydride is limited, while chemical preparation condition harshness, complex process, the cost height has limited the development of polyimide material to a great extent.In actual application, polyimide material must have the property and the function that can satisfy the special applications purpose on existing excellent comprehensive performances basis; For example, as super large-scale integration and microelectronic packaging material, polyimide material also must have advantages such as high resolution, low-hygroscopicity, low-expansion coefficient, low mold temperature except performances such as the high heat-resistant stability that must have, strong mechanical performance, high electric insulation, low-k, low-dielectric loss; Therefore, for satisfying the specific demand of high-technology field, people always at the novel monomeric of constantly researching and developing polyimide, comprise organic tetracarboxylic dianhydride of aromatic series and aromatic diamine etc. in recent years.US Patent5274126 discloses a kind of synthetic method that contains the fluorine-containing tetracarboxylic dianhydride of two hexafluoro sec.-propyls; People such as B.Y.Myung [B.Y.Myung, J.J.Kim, T.H.Yoon.J.Poly.Sci.Part A:Polym.Chem.Ed, 2002,40,4217-4227] have reported 1,2,4 of a kind of fluoro-containing group replacement, the preparation method and its usage of 5-pyromellitic acid dianhydride; People such as C.P.Yang [C.P.Yang, R.S.Chen, K.H.Chen, J.Polym.Sci.Part A:Polym.Chem.Ed, 2003,41,922-938] reported a kind of aromatic diamine monomer that contains trifluoromethyl, 2, the preparation method of two [4-(4-amido-2-4-trifluoromethylphenopendant) the phenyl]-HFC-236fa of 2-, this monomer has high reaction activity and high, has high second-order transition temperature (265 ℃) and low specific inductivity 2.68 (1MHz) with 6FDA through the polyimide material of condensation reaction preparation, has good solubility property and good optical through performance simultaneously.
Summary of the invention
The invention discloses organic tetracarboxylic dianhydride of a kind of fluorinated aromatic and derivative thereof, polyimide material prepared therefrom not only has the excellent comprehensive performance, as high heat-resistant stability, high mechanics mechanical property, high glass-transition temperature, high electric insulation performance, low-k and dielectric loss, have good solubility property and very low moisture absorption ratio simultaneously; It is dissolved in the organic solvent polyimide resin solution that can obtain highly filled, low viscosity, has excellent storage stability.This polymers soln is coated on the surface of glass (or silicon single crystal, pottery) substrate,, can obtains high strength, high transparent polyimide coating or film through the suitable processing that is heating and curing.Therefore, having important use at high-technology fields such as microelectronics Packaging and space flight, aviations is worth.
Organic tetracarboxylic dianhydride of fluorinated aromatic of the present invention and derivative thereof, its chemical structure be as shown in Equation 1:
The invention also discloses a kind of method for preparing organic tetracarboxylic dianhydride of above-mentioned fluorinated aromatic and derivative thereof, its reaction formula is suc as formula 2:
The steps include:
1) 60-80 part trifluoroacetate, 1-30 part magnesium powder, 130-150 part replacement halobenzene and 150-500 part tetrahydrofuran (THF) stirred backflow 1-4 hour down, with the sulphuric acid hydrolysis of 10-30%, collected organic phase, distilled to obtain a, a, a-trifluoromethyl acetophenone liquid;
Described trifluoroacetate comprises trifluoroacetic acid potassium, trifluoroacetic acid lithium, sodium trifluoroacetate, trifluoroacetic acid magnesium or trifluoroacetic acid aluminium.
Described replacement halobenzene comprises bromobenzene, m-trifluoromethyl phenyl-bromide, to methyl bromobenzene trifluoride, p-Fluoro bromo benzene, 3,5-two methyl bromobenzene trifluorides, chlorobenzene, m-trifluoromethyl chlorobenzene, to the trifluoromethyl chlorobenzene, to fluorochlorobenzene, 3,5-two trifluoromethyl chlorobenzenes, iodobenzene, m-trifluoromethyl iodobenzene, to trifluoromethyl iodobenzene, to fluorine iodobenzene, 3,5-two trifluoromethyl iodobenzenes, fluorobenzene, m-trifluoromethyl fluorobenzene, to trifluoromethyl-fluorobenzene, 1,4-two fluorobenzene or 3,5-two trifluoromethyl-fluorobenzenes.
2) in the nitrogen atmosphere, product liquid 50-80 part that step 1 is obtained and 300-500 part o-Xylol, 15-40 part strong acid stirring reaction 10-100 hour boil off o-Xylol, obtain the fluorinated aromatic tetramethyl compound;
Described strong acid comprises methylsulphonic acid, tosic acid, trifluoromethanesulfonic acid, trifluoromethyl Phenylsulfonic acid, hydrochloric acid, oleum or nitric acid.
3) the product 30-50 part that step 2 is obtained, 800-1200 part 10-30% nitric acid or 150-300 part KMnO
4In reactor, reflux and stirred 1-7 hour, cooling is filtered, and obtains the organic tetracid of fluorinated aromatic after the drying;
4) product that step 3 is obtained is heated to 180-220 ℃ of dehydration, obtains organic tetracarboxylic dianhydride of fluorinated aromatic and derivative thereof.
The described dehydration of step 4 can also be: every part of step 3 obtains in the acetic anhydride/acetic acid mixed solvent that product adds 2-4 part stirring and refluxing 2-6 hour, and the ratio of mixed solvent is 2 parts of diacetyl oxides: 1 part of acetate; Boil off solvent, cooling is filtered, dry back o-Xylol recrystallization, and oven dry obtains organic tetracarboxylic dianhydride of fluorinated aromatic and derivative thereof.
Can be used for preparing polyimide material by organic tetracarboxylic dianhydride of fluorinated aromatic provided by the invention and derivative thereof with aromatic diamine, its chemical structure of the polyimide material of preparation as shown in Equation 3:
Above-mentioned polyimide material, its preparation process is:
A) every part of organic solvent that the aromatic series organic diamine adds 5-20 part, dissolving, in the organic tetracarboxylic dianhydride of fluorinated aromatic and the derivative thereof of 0-4 ℃ of adding and aromatic series organic diamine equal portions, under the room temperature nitrogen protection stirring reaction 10-24 hour, obtain polyamic acid solution;
Described aromatic diamine is meant the aromatic organic compounds that contains two amidos, comprise Ursol D (p-PDA), mphenylenediamine (m-PDA), 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), 3-trifluoromethyl-4,4 '-diamines yl diphenyl ether (3FODA), 4,4 '-two (4-amido phenoxy group) benzene (APB), 4,4 '-two (2,2 '-two trifluoromethyls-4-amido phenoxy group) benzene (6FAPB), 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS), 4,4 '-diaminodiphenylmethane (MDA), 1, two (4-the aminocarbonyl phenyl)-1-(3-trifluoromethyl)-2,2 of 1-, 2-Halothane (6FDAM) etc. and arbitrary proportion blended mixture thereof.
B) polyamic acid solution is coated in the surface of glass or silicon chip, is heated to 250-350 ℃, make polyamic acid be converted into polyimide material; Perhaps
Acetyl acid anhydride/pyridine mixing solutions of 1: 1 is under agitation added in the polyamic acid solution of step a preparation, the amount of acetyl acid anhydride/pyridine mixing solutions is equivalent to organic tetracarboxylic dianhydride of fluorinated aromatic and derivative amount thereof 4-5 times, be warming up to 40-60 ℃ of reaction 3-8 hour, after being cooled to room temperature, in organic alcohol solvent, the 60-100 that the amount of organic alcohol solvent is equivalent to organic tetracarboxylic dianhydride of fluorinated aromatic and derivative amount thereof doubly with the liquid dispersion that obtains; Collecting precipitation and with organic alcohol solvent washing, 40-60 ℃ of drying obtains the polyimide solid resin; This polyimide solid resin is mixed with organic solvent, treat its all dissolving after-filtration, obtain polyimide coating glue; Polyimide solution is coated on glass or the monocrystalline silicon surface, and heat temperature raising obtains polyimide coating or film to 200-250 ℃.
Above-mentioned organic solvent is N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, gamma-butyrolactone or methyl-sulphoxide and mixed solvent arbitrarily thereof.
The present invention prepares the polyimide material of gained, and good solubility property is arranged, and not only dissolves in strong polar aprotic organic solvent, comprises N-Methyl pyrrolidone, N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide, dimethyl sulfoxide (DMSO); Dissolve in simultaneously that some are common, lower boiling, low polar ordinary organic solvents, comprise gamma-butyrolactone, cyclopentanone, tetrahydrofuran (THF), dioxane, methyl acetate.To be dissolved in by the polyimide solid resin of chemical imidization method gained in the suitable organic solvent system, can obtain the polyimide resin solution that solids content surpasses 20wt%, adopt then and get rid of methods such as the method for being coated with, pickling process, spraying method or silk screen printing and be coated on the substrate, after adding the heat extraction solvent, can obtain flexible polymeric film.
Polyimide resin of the present invention has excellent comprehensive performances; having important use in microelectronics Packaging is worth; typically used comprises, the interlayer dielectric insulating layer film of surperficial chip passivation layer, stress buffer undercoat, contact protective membrane, multilayer interconnection circuit, the liquid crystal molecular orientation film in the lcd technology and high temperature resistant binder etc.
Embodiment
Following embodiment 1-5 is the preparation organic tetracarboxylic dianhydride of fluorinated aromatic and a derivative thereof, and embodiment 7-15 is to be the feedstock production polyimide with organic tetracarboxylic dianhydride of fluorinated aromatic and derivative thereof.
Example 1
α, α, the preparation of α-trifluoromethyl acetophenone: mechanical stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding 20 parts in magnesium powder, 60 parts in trifluoroacetic acid potassium, 400 parts of tetrahydrofuran (THF)s under agitation drip 130 parts of bromobenzenes.Reaction mixture under agitation refluxed 2-3 hour, obtained black gray turbid solution, the sulphuric acid soln hydrolysis with 15%.Collect organic phase, water dichloromethane extraction three times merge organic phase, anhydrous sodium sulfate drying, and distillation obtains colourless α, α, α-trifluoromethyl acetophenone liquid.
1, two (3, the 4-the 3,5-dimethylphenyl)-1-phenyl-2 of 1-, 2, the preparation of 2-Halothane: with 70 parts of α, α, α-trifluoromethyl acetophenone, 300 parts of o-Xylols and 30 parts of methylsulphonic acids add in the there-necked flask of band import and export of nitrogen, and induction stirring reaction 72 hours boils off o-Xylol.Product gets white 1 with the benzene recrystallization, two (3, the 4-the 3,5-dimethylphenyl)-1-phenyl-2,2 of 1-, 2-Halothane.
1, two (3,4-dicarboxyl the phenyl)-1-phenyl-2,2 of 1-, the preparation of 2-Halothane: with 40 part 1, two (3, the 4-the 3,5-dimethylphenyl)-1-phenyl-2 of 1-, 2,2-Halothane, 500 parts of pyridines and 150 parts of water add in the 2000ml there-necked flask, after heated and stirred refluxes with 240 parts of KMnO
4Add in the there-necked flask in batches, and then reflux and stirred 4 hours.Cold filtration is except that the manganese dioxide precipitate of black removal.Collect filtrate, boil off whole pyridines and most of water, gained solution adds in the 2000ml there-necked flask again, adds sodium hydroxide and 500 parts of water of 106 parts again, after the reflux with 170 parts of KMnO
4Add in the there-necked flask in batches, add in 5 hours.Continue to reflux 2 hours, after the cooling, drip 20 parts of methyl alcohol slightly, keep refluxing about 2 hours, take advantage of heat filtering.The filtrate distillation is concentrated into 150 parts, is acidified to pH value with HCl and equals 2.Filter, filter cake with dilute hydrochloric acid give a baby a bath on the third day after its birth time, washing three times, place vacuum oven, obtain white 1, two (3,4-dicarboxyl the phenyl)-1-phenyl-2,2 of 1-, 2-Halothane.
The preparation of 4,4 '-(1-phenyl-2,2,2-Halothane base) two O-phthalic acid dianhydrides: with 30 part 1, two (3,4-dicarboxyl the phenyl)-1-phenyl-2,2 of 1-, 2-Halothane, 120 parts of diacetyl oxides and 60 parts of glacial acetic acids add in the 250ml there-necked flask, and the stirring and refluxing reaction boiled off most of solvent after 4 hours, cooling is separated out solid, suction filtration, the o-Xylol recrystallization is used in dry back, and vacuum drying gets white 4,4 '-(1-phenyl-2,2,2-Halothane base) two O-phthalic acid dianhydride solids.
Example 2
3-trifluoromethyl-α, α, the preparation of α-trifluoromethyl acetophenone: mechanical stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, add 30 parts in magnesium powder, 80 parts of trifluoroacetic acid lithiums, 600 parts of anhydrous diethyl ethers under agitation drip 150 parts of 3-trifluoromethyl chlorobenzenes.Reaction mixture under agitation refluxed 2-3 hour, obtained black gray turbid solution, the sulphuric acid soln hydrolysis with 20%.The collection organic phase, water extracted with diethyl ether three times merge organic phase, and 152-154 ℃ of cut collected in distillation, gets colourless 3-trifluoromethyl-α, α, α-trifluoromethyl acetophenone liquid.
1,1-two (3, the 4-3,5-dimethylphenyl)-1-(3-trifluoromethyl)-2,2, the preparation of 2-Halothane: with 90 parts of 3-trifluoromethyl-α, α, α-trifluoromethyl acetophenone, 350 parts of o-Xylols and 35 parts add the methylbenzene methylsulfonic acid in the there-necked flask of band import and export of nitrogen, induction stirring reaction 72 hours boils off o-Xylol.Product gets white 1 with the benzene recrystallization, two (3, the 4-the 3,5-dimethylphenyl)-1-(3-trifluoromethyl)-2,2 of 1-, 2-Halothane.
1,1-two (3,4-dicarboxyl phenyl)-1-(3-trifluoromethyl)-2,2, the preparation of 2-Halothane: with 45 part 1,1-two (3, the 4-3,5-dimethylphenyl)-1-(3-trifluoromethyl)-2,2, the salpeter solution of 2-Halothane and 1000 part 20% adds in the 2000ml autoclave, and pressurize refluxes and stirred 4 hours.Take advantage of heat to pour out, white solid is separated out in cooling.Filter, filter cake with dilute hydrochloric acid give a baby a bath on the third day after its birth time, washing three times, place vacuum oven, white 1, two (3,4-dicarboxyl the phenyl)-1-(3-trifluoromethyl)-2,2 of 1-, 2-Halothane.
4,4 '-[1-(3-trifluoromethyl)-2,2,2-Halothane base] preparation of two O-phthalic acid dianhydrides: with 40 part 1, two (3,4-dicarboxyl the phenyl)-1-(3-trifluoromethyl)-2,2 of 1-, the 2-Halothane is heated to 180-190 ℃ under vacuum, remove the moisture of generation, obtain 4,4 '-[1-(3-trifluoromethyl)-2 after the cooling, 2,2-Halothane base] two O-phthalic acid dianhydrides.
Example 3
4-trifluoromethyl-α, α, the preparation of α-trifluoromethyl acetophenone: mechanical stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, add 20 parts in magnesium powder, 80 parts of sodium trifluoroacetates, 450 parts of tetrahydrofuran (THF)s under agitation drip 150 parts of 4-methyl bromobenzene trifluorides.Reaction mixture under agitation refluxed 2-3 hour, obtained black gray turbid solution, the sulphuric acid soln hydrolysis with 10%.Collect organic phase, water merges organic phase with extracted with diethyl ether three times, anhydrous sodium sulfate drying, distill colourless 4-trifluoromethyl-α, α, α-trifluoromethyl acetophenone liquid.
1,1-two (3, the 4-3,5-dimethylphenyl)-1-(4-trifluoromethyl)-2,2, the preparation of 2-Halothane: with 80 parts of 4-trifluoromethyl-α, α, α-trifluoromethyl acetophenone, 400 parts of o-Xylols and 40 parts of trifluoromethanesulfonic acids add in the there-necked flask of band import and export of nitrogen, induction stirring reaction 72 hours boils off o-Xylol.Product gets white 1 with the benzene recrystallization, two (3, the 4-the 3,5-dimethylphenyl)-1-(4-trifluoromethyl)-2,2 of 1-, 2-Halothane.
1,1-two (3,4-dicarboxyl phenyl)-1-(4-trifluoromethyl)-2,2, the preparation of 2-Halothane: with 45 part 1,1-two (3, the 4-3,5-dimethylphenyl)-1-(4-trifluoromethyl)-2,2,2-Halothane, 500 parts of pyridines and 150 parts of water add in the 2000ml there-necked flask, after heated and stirred refluxes with 250 parts of KMnO
4In 4 hours, add in the there-necked flask in batches, and then reflux and stirred 2 hours.Cold filtration is except that the manganese dioxide precipitate of black removal.Collect filtrate, boil off whole pyridines and most of water, gained solution adds in the 2000ml there-necked flask again, adds 56 parts of sodium hydroxide and 500 parts of water again, after the reflux with 157 parts of KMnO
4Add in the there-necked flask in batches, add in 5 hours.Continue to reflux 2 hours, after the cooling, drip 20 parts of methyl alcohol slightly, keep refluxing about 2 hours, take advantage of heat filtering.The filtrate distillation is concentrated into 150 parts, is acidified to pH value with HCl and equals 2.Filter, filter cake with dilute hydrochloric acid give a baby a bath on the third day after its birth time, washing three times, place vacuum oven.White 1, two (3,4-dicarboxyl the phenyl)-1-(4-trifluoromethyl)-2,2 of 1-, 2-Halothane.
4,4 '-[1-(4-trifluoromethyl)-2,2,2-Halothane base] preparation of two O-phthalic acid dianhydrides: with 40 part 1,1-two (3,4-dicarboxyl phenyl)-1-(4-trifluoromethyl)-2,2,2-Halothane, 140 parts of diacetyl oxides and 70 parts of glacial acetic acids add in the 250ml there-necked flask, and the stirring and refluxing reaction is after 4 hours, boil off most of solvent, cooling is separated out solid, suction filtration, dry back o-Xylol recrystallization, vacuum drying gets white 4,4 '-[1-(4-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydride solids.
Example 4
4-fluoro-α, α, the preparation of α-trifluoromethyl acetophenone: mechanical stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding 25 parts in magnesium powder, 80 parts in trifluoroacetic acid magnesium, 450 parts of tetrahydrofuran (THF)s under agitation drip 135 parts of 3-methyl bromobenzene trifluorides.Reaction mixture under agitation refluxed 2-3 hour, obtained black gray turbid solution, the sulphuric acid soln hydrolysis with 10%.Collect organic phase, water merges organic phase with extracted with diethyl ether three times, anhydrous sodium sulfate drying, distillation collect 4-fluoro-α, α, α-trifluoromethyl acetophenone liquid.
1,1-two (3, the 4-3,5-dimethylphenyl)-1-(4-fluorophenyl)-2,2, the preparation of 2-Halothane: with 90 parts of 4-fluoro-α, α, α-trifluoromethyl acetophenone, 500 parts of o-Xylols and 50 parts of trifluoromethanesulfonic acids add in the there-necked flask of band import and export of nitrogen, induction stirring reaction 72 hours boils off o-Xylol.Product gets white 1 with the benzene recrystallization, two (3, the 4-the 3,5-dimethylphenyl)-1-(4-fluorophenyl)-2,2 of 1-, 2-Halothane.
1,1-two (3,4-dicarboxyl phenyl)-1-(4-fluorophenyl)-2,2, the preparation of 2-Halothane: with 38 part 1,1-two (3, the 4-3,5-dimethylphenyl)-1-(3-trifluoromethyl)-2,2,2-Halothane, 500 parts of pyridines and 150 parts of water add in the 2000ml there-necked flask, after heated and stirred refluxes with 255 parts KMnO
4In 4 hours, add in the there-necked flask in batches, and then reflux and stirred 2 hours.Cold filtration is except that the manganese dioxide precipitate of black removal.Collect filtrate, boil off whole pyridines and most of water, gained solution adds in the 2000ml there-necked flask again, adds sodium hydroxide and 500 parts of water of 60 parts again, after the reflux with 157 parts of KMnO
4Add in the there-necked flask in batches, add in 5 hours.Continue to reflux 2 hours, after the cooling, drip 20ml methyl alcohol slightly, keep refluxing about 2 hours, take advantage of heat filtering.The filtrate distillation is concentrated into 150 parts, is acidified to pH value with HCl and equals 2.Filter, filter cake with dilute hydrochloric acid give a baby a bath on the third day after its birth time, washing three times, place vacuum oven, white 1, two (3,4-dicarboxyl the phenyl)-1-(4-fluorophenyl)-2,2 of 1-, 2-Halothane.
4,4 '-[1-(4-fluorophenyl)-2,2,2-Halothane base] preparation of two O-phthalic acid dianhydrides: with 30 part 1,1-two (3,4-dicarboxyl phenyl)-1-(3-trifluoromethyl)-2,2,2-Halothane, 120 parts of diacetyl oxides and 60 parts of glacial acetic acids add in the 250ml there-necked flask, and the stirring and refluxing reaction is after 4 hours, boil off most of solvent, cooling is separated out solid, suction filtration, dry back o-Xylol recrystallization, vacuum drying gets white 4,4 '-[1-(4-fluorophenyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides.
Example 5
3,5-two trifluoromethyls-α, α, the preparation of α-trifluoromethyl acetophenone: mechanical stirring is being housed, in the there-necked flask of prolong and import and export of nitrogen, is adding 20 parts in magnesium powder, 60 parts in trifluoroacetic acid aluminium, 250 parts of tetrahydrofuran (THF)s under agitation drip 3,146 parts of 5-two trifluoromethyl-fluorobenzenes.Reaction mixture under agitation refluxed 2-3 hour, obtained black gray turbid solution, the sulphuric acid soln hydrolysis with 10%.Collect organic phase, water merges organic phase with extracted with diethyl ether three times, and anhydrous sodium sulfate drying distills colourlessly 3,5-two trifluoromethyls-α, α, α-trifluoromethyl acetophenone liquid.
1,1-two (3, the 4-3,5-dimethylphenyl)-1-(3,5-two trifluoromethyls)-2,2, the preparation of 2-Halothane: with 70 part 3,5-two trifluoromethyls-α, α, α-trifluoromethyl acetophenone, 300 parts of o-Xylols and 30 parts of trifluoromethylbenzene methylsulfonic acids add in the there-necked flask of band import and export of nitrogen, induction stirring reaction 72 hours boils off o-Xylol.Product gets white 1 with the benzene recrystallization, two (3, the 4-the 3,5-dimethylphenyl)-1-(3,5-two trifluoromethyls)-2,2 of 1-, 2-Halothane.
1, two (3,4-dicarboxyl the phenyl)-1-(3,5-two trifluoromethyls)-2 of 1-, 2, the preparation of 2-Halothane: with 40 part 1, two (3, the 4-the 3,5-dimethylphenyl)-1-(3 of 1-, 5-two trifluoromethyls)-2,2, the salpeter solution that the 2-Halothane is 1000 part 20% adds in the 2000ml autoclave, and pressurize refluxes and stirred 4 hours.Take advantage of heat to pour out, white solid is separated out in cooling.Filter, filter cake with dilute hydrochloric acid give a baby a bath on the third day after its birth time, washing three times, place vacuum oven.White 1, two (3,4-dicarboxyl the phenyl)-1-(4-trifluoromethyl)-2,2 of 1-, 2-Halothane.
4,4 '-[1-(3,5-two trifluoromethyls)-2,2,2-Halothane base] preparation of two O-phthalic acid dianhydrides: with 30 part 1,1-two (3,4-dicarboxyl phenyl)-1-(3,5-two trifluoromethyls)-2,2, the 2-Halothane is heated to 170-180 ℃ under vacuum, remove the moisture of generation simultaneously, obtain white 4,4 '-[1-(4-trifluoromethyl)-2 after the cooling, 2,2-Halothane base] two O-phthalic acid dianhydride solids.
Example 6
40 parts of Ursol D (p-PDA) are added in 230 parts of N-Methyl pyrrolidone; After treating that solid all dissolves, under 0-4 ℃, add 40 part 4,4 '-[1-phenyl-2,2,2-Halothane base] two O-phthalic acid dianhydrides in batches.Be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase thick liquid.10 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 2000 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 solid resins, add 180 parts of N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide solution.Polyimide solution is coated in glass pane surface, handles through following programmed heating: 80 ℃ were heated 1 hour, and 120 ℃ kept 1 hour down, and 200 ℃ kept 1 hour, and 250 ℃ kept 0.5 hour; After heat treated is finished, sheet glass is immersed in the water, peel off and obtain Kapton.
Example 7
60 parts of mphenylenediamines (m-PDA) are added 450 parts of N, dinethylformamide, after treating to dissolve fully, under 0-4 ℃, add 60 part 4 in batches, 4 '-[1-(3-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.Polyamic acid solution is coated on the glass surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour, and 275～300 ℃ kept 1 hour; Sheet glass is immersed in the water, peel off and obtain Kapton.
Example 8
With 30 part 4,4 '-ether diamine (4,4-ODA) add in 250 parts of N-Methyl pyrrolidone, treat that solid dissolves fully after, adds 1 part pair-(γ-aminopropyl) tetramethyl-silica alkane; Add 30 part 4 under 0-4 ℃, 4 '-[1-(3-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides are reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution in batches.Polyamic acid solution is coated on the glass surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour, and 275～300 ℃ kept 1 hour; Sheet glass is immersed in the water, peel off and obtain Kapton.
Example 9
With 50 part 3,4-diamines yl diphenyl ether (3,4 '-ODA) adds in 500 parts of N-Methyl pyrrolidone, after treating to dissolve fully, under 0-4 ℃, add 50 part 4,4 '-[1-(4-fluorophenyl)-2 in batches, 2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.200 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 5000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 120 parts of dried solid resins, add 900 parts of N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide resin solution.Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 0.5 hour, and 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
With 30 parts of 3-trifluoromethyls-4,4 '-diamines yl diphenyl ether (3FODA) adds in 250 parts of N-Methyl pyrrolidone, treat that solid dissolves fully after, adds 1 part pair-(γ-aminopropyl) tetramethyl-silica alkane; Add 30 part 4 under 0-4 ℃, 4 '-[1-(3-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides are reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution in batches.Polyamic acid solution is coated on the glass surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour, and 275～300 ℃ kept 1 hour; Sheet glass is immersed in the water, peel off and obtain Kapton.
Example 11
With 50 part 4,4 '-two (4-amido phenoxy group) benzene (APB) adds 400 parts of N, in the N-N,N-DIMETHYLACETAMIDE, after treating to dissolve fully, under 0-4 ℃, add 50 part 4,4 '-[1-(4-trifluoromethyl)-2 in batches, 2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.Polyamic acid solution is coated on the glass surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour, and 275～300 ℃ kept 1 hour; Sheet glass is immersed in the water, peel off and obtain Kapton.
Example 12
With 25 part 4,4 '-two (2,2 '-two trifluoromethyls-4-amido phenoxy group) benzene (6FAPB) adds in 450 parts of N-Methyl pyrrolidone, after treating to dissolve fully, adds 25 part 4 under 0-4 ℃ in batches, 4 '-[1-(3,5-two trifluoromethyls)-2,2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.110 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 5000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 120 parts of dried solid resins, add 900 parts of N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide resin solution.Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 0.5 hour, and 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 13
With 50 part 4,4 '-diaminodiphenylsulfone(DDS) (4,4 '-DDS) adds in 550 parts of N-Methyl pyrrolidone, after treating to dissolve fully, adds 50 part 4 under 0-4 ℃ in batches, 4 '-[1-(3,5-two trifluoromethyls)-2,2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.250 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 5000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 120 parts of dried solid resins, add 900 parts of N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide resin solution.Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 0.5 hour, and 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 14
With 70 part 4,4 '-diaminodiphenylmethane (MDA) adds in 400 parts of N-Methyl pyrrolidone, after treating to dissolve fully, under 0-4 ℃, add 70 part 4 in batches, 4 '-[1-(4-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.Polyamic acid solution is coated on the glass surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 1 hour, and 275～300 ℃ kept 1 hour; Sheet glass is immersed in the water, peel off and obtain Kapton.
Example 15
With 60 part 1, two (4-the aminocarbonyl phenyl)-1-(3-trifluoromethyl)-2 of 1-, 2,2-Halothane (6FDAM) adds in 450 parts of N-Methyl pyrrolidone, after treating to dissolve fully, under 0-4 ℃, add 60 part 4 in batches, 4 '-[1-(3-trifluoromethyl)-2,2,2-Halothane base] two O-phthalic acid dianhydrides, be reflected at and carried out under 20-25 ℃ 24 hours, obtain the homogeneous phase polyamic acid solution.240 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 4000 parts of ethanol, collects the solid of separating out, use methanol wash 3 times, 40-60 ℃ of following vacuum-drying.Take by weighing 120 parts of dried solid resins, add 1000 parts of N, N '-N,N-DIMETHYLACETAMIDE.Treat that solid all dissolves after-filtration, obtains polyimide resin solution.Polymers soln is coated on the semiconductor chip surface, and in 100 ℃ of heating 1 hour, 200 ℃ kept 1 hour down, and 250 ℃ kept 0.5 hour, and 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 (7)
1. fluorinated aromatic tetracarboxylic dianhydride and derivative thereof, structure as shown in the formula:
2. method for preparing organic tetracarboxylic dianhydride of the described fluorinated aromatic of claim 1 and derivative thereof, its reaction as shown in the formula:
The steps include:
A) tetrahydrofuran (THF) of the replacement halobenzene of the magnesium powder of the trifluoroacetate of 60-80 weight part, 1-30 weight part, 130-150 weight part and 150-500 weight part stirred backflow 1-4 hour down, with the sulphuric acid hydrolysis of 10%-30%, collect organic phase, distillation obtains a, a, a-trifluoromethyl acetophenone liquid;
B) in the nitrogen atmosphere, product liquid 50-80 weight part and strong acid stirring reaction 300-500 o-Xylol, 15-40 weight part that step a is obtained 10-100 hour boils off o-Xylol, obtains the fluorinated aromatic tetramethyl compound;
C) the product 30-50 weight part that step b is obtained, the 10-30% nitric acid of 800-1200 weight part or the KMnO of 150-300 weight part
4In reactor, reflux and stirred 1-7 hour, cooling is filtered, and obtains the organic tetracid of fluorinated aromatic after the drying;
D) product that step c is obtained is heated to 180-220 ℃ of dehydration, obtains organic tetracarboxylic dianhydride of fluorinated aromatic and derivative thereof.
3. preparation method according to claim 2, it is characterized in that, the described dehydration of steps d can also be: every part of step c obtain product add the 2-4 weight part the acetic anhydride/acetic acid mixed solvent in stirring and refluxing 2-6 hour, the ratio of mixed solvent is the diacetyl oxide of 2 weight parts: the acetate of 1 weight part; Boil off solvent, cooling is filtered, dry back o-Xylol recrystallization, and oven dry obtains organic tetracarboxylic dianhydride of fluorinated aromatic and derivative thereof.
4. preparation method according to claim 2 is characterized in that, the described trifluoroacetate of step a comprises trifluoroacetic acid potassium, trifluoroacetic acid lithium, sodium trifluoroacetate, trifluoroacetic acid magnesium or trifluoroacetic acid aluminium.
5. preparation method according to claim 2, it is characterized in that, the described replacement halobenzene of step a comprises bromobenzene, m-trifluoromethyl phenyl-bromide, to methyl bromobenzene trifluoride, p-Fluoro bromo benzene, 3,5-two methyl bromobenzene trifluorides, chlorobenzene, m-trifluoromethyl chlorobenzene, to the trifluoromethyl chlorobenzene, to fluorochlorobenzene, 3,5-two trifluoromethyl chlorobenzenes, iodobenzene, m-trifluoromethyl iodobenzene, to trifluoromethyl iodobenzene, to fluorine iodobenzene, 3,5-two trifluoromethyl iodobenzenes, fluorobenzene, m-trifluoromethyl fluorobenzene, to trifluoromethyl-fluorobenzene, 1,4-two fluorobenzene or 3,5-two trifluoromethyl-fluorobenzenes.
6. preparation method according to claim 2 is characterized in that, the strong acid in the described preparation process comprises methylsulphonic acid, tosic acid, trifluoromethanesulfonic acid, trifluoromethyl Phenylsulfonic acid, hydrochloric acid, oleum or nitric acid.
7. fluorine-containing organic tetracarboxylic dianhydride according to claim 1 and derivative thereof are used to prepare aromatic polyimide.
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| CN100569833C (en) * | 2006-04-28 | 2009-12-16 | 中国科学院化学研究所 | A kind of fluorine-containing thermoplastic polyimide polymer and preparation method thereof |
| KR101613753B1 (en) * | 2008-10-07 | 2016-04-19 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid crystal aligning agent and liquid crystal display element using same |
| CN103224447A (en) * | 2013-03-27 | 2013-07-31 | 巨化集团技术中心 | Preparation method of trifluoromethyl ketone |
| EP3597627A1 (en) * | 2014-10-14 | 2020-01-22 | Syngenta Participations AG | Process for the preparation of 1-(3,5-dichlorophenyl)-2,2,2-trifluoroethanone and derivatives thereof |
| CN109438470A (en) * | 2018-12-24 | 2019-03-08 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of thiophene and its synthetic method and application |
| CN112028752B (en) * | 2020-09-28 | 2023-02-03 | 台州臻挚生物科技有限公司 | Synthetic method of 3',5' -dichloro-2, 2-trifluoroacetophenone |
| WO2022061917A1 (en) * | 2020-09-28 | 2022-03-31 | 台州臻挚生物科技有限公司 | Synthesis method for 3',5'-dichloro-2,2,2-trifluoroacetophenone |
| CN112110790B (en) * | 2020-09-28 | 2023-06-23 | 台州臻挚生物科技有限公司 | Preparation method of 3, 5-dihalide benzotrifluoride and 3 '-chloro-5' -trifluoromethyl phenyl trifluoro-ethanone |
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| US5166204A (en) * | 1989-11-01 | 1992-11-24 | Toyama Chemical Co., Ltd. | Isoindole derivatives and salts thereof and antitumor agent comprising the same |
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| US5166204A (en) * | 1989-11-01 | 1992-11-24 | Toyama Chemical Co., Ltd. | Isoindole derivatives and salts thereof and antitumor agent comprising the same |
Non-Patent Citations (2)
| Title |
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| New reactivity of stable indole-2,3-quinodimethaneequivalents : [4+2]-cycloaddition , cycloreversion , sigmatropicrearrangement, and elimination processes in the reactions of1,4-dimethylpyrano [3,4-b] indol-3-one and 1-methylpyrido[3,4-b] indol-3-one with. Erfanian-Abdoust , Houshang , Pindur, Ulf.Heterocycles,Vol.29 No.9. 1709 * |
| Synthesis and Diels-Alder reactions of the furo [3,4-b] pyrrolering system. A new indole ring synthesis. Moskalev, Nikolai V. et al.Tetrahedron Letters,Vol.43 No.2. 2002 * |
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