CN1436815A - Prepn of lateral hydroxyl group containing polyimide/SiO2 hybrid film - Google Patents
Prepn of lateral hydroxyl group containing polyimide/SiO2 hybrid film Download PDFInfo
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Abstract
The preparation process of lateral hydroxyl group containing polyimide/SiO2 hybrid film includes dissolving polyamido acid containing lateral hydroxyl group or polyimide in 1-1400 portions in solvent to compound 5-15 % concentration solution, adding silane coupling agent containing epoxy radical in 0-250 portions for reaction at 120-150 deg.c in the presence of catalyst in 0.1-10 portions of 2-4 hr; cooling to room temperature, adding n-silicate ester in 1-1000 portions through stirring for 6-24 hr, flow casting to form film, and processing at 0.1 atm negative pressure and 60 deg.c for 12 hr, and 160 deg.C for 2 hr, at 200 deg.c for 2 hr, at 260 deg.c for 1 hr and at 300 deg.c for 0.5 hr to obtain the lateral hydroxyl group containing polyimide/SiO2 hybrid film.
Description
One, technical field
The present invention relates to a kind of preparation method of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film, belong to the synthetic and preparation field of organic-inorganic hybrid material.
Two, background technology
In recent years, along with the widespread use of large-scale integrated circuit, super large-scale integration, electronic and electrical equipment is towards miniaturization, integrated, high-power and high reliability development, to the demands for higher performance of polyimide., characteristics such as specific inductivity little, electrical insulating property good, good film-forming property high temperature resistant except needing require also that material has that coefficient of thermal expansion is low, water-intake rate is low, degree of polarization is little, performance such as high strength, high-modulus, chemical proofing are good.The inaccessible above-mentioned requirements of the over-all properties of common polyimide has greatly limited its application in hyundai electronics industry.Compare with polyimide, silicon-dioxide has better heat-resisting and mechanical property, and thermal expansivity is extremely low, is about 3 * 10
-6K
-1(Sachdev; Krishna Gandhe, et a1., USP 5976710), physics and chemical stability are all fine; But its forming process is poor, is difficult to large-scale promotion application.
From the nineties in 20th century, the foreign scholar has launched research to the polyimide/silicon dioxide hybrid film, and purpose prepares a kind of advantage that has polyimide and silicon-dioxide concurrently, the novel film material of excellent combination property.Nandi etc. are raw material with the tetrol salt of pyromellitic dianhydride, phenyl ether diamines and titanium or silicon, method by sol-gel has prepared polyimide/metal oxide hybrid material (M.Nandi, J.A.Conklin., et al., Chem.Mater., 1990.2:772); The Atsushi of Japan etc. has done systematic study (A.Morikawa, Y.Iyoku, M.Kakimoto.Polym.Jour., 1992,24 (1): 107) to the performance of various polyimide/silicon dioxide organic/inorganic hybridization materials; Petrsysel etc. have analyzed interaction (P.Sysel, M.Maryska .Polym.Jour., 1997,29 (7): 607) between organic and inorganic component in the polyimide/silicon dioxide hybrid film; Yan etc. are by the end capped method of amino silicane coupling agent, make the hybrid film of intensity between 80～100MPa (C.Yan, O.I.Jude, Chem.Mater., 1999,11:1218); Ging etc. to the over-all properties of end of the chain modified polyimide/SiO 2 hybrid film carried out exploring (H.H.Ging, C.K.Jem, L.L.Ying, J.Appl.Polym.Sci., 2000,76:1699).
Former research results shows that common polyimide/silicon dioxide hybrid material greater than 8% o'clock, makes hybridized film no longer transparent owing to be separated at dioxide-containing silica, and inorganic phase size reaches several microns; And silicon-dioxide phase particle size further increases with the increase of inorganic component content, and the trend of mutual reunion is arranged, and takes place significantly to be separated, and the hybrid material transparency, mechanical property are further descended.The reason that causes this situation is that polyimide has very large stiff backbone structure usually, and is very weak with inorganic interaction mutually; And the inorganic particulate specific surface area of nanoscale is big, the surface energy height, and adsorption is very strong, is easy to generate reunion.
Three, summary of the invention
The objective of the invention is to provide a kind of preparation method of polyimide/silicon dioxide hybrid film of lateral hydroxyl group containing at the deficiencies in the prior art.It is to prepare by sol gel reaction by the polyamic acid that contains active lateral hydroxyl group or polyimide and positive silicon ester or with silane coupling agent that contains epoxy group(ing) and positive silicon ester.Lateral hydroxyl group can or form hydrogen bond with the copolycondensation of silicon hydroxyl, utilize the ring-opening reaction of lateral hydroxyl group and epoxy group(ing) and the cohydrolysis of silane coupling agent and positive silicon ester simultaneously, between polyimide and silicon-dioxide, introduce chemically crosslinked or strong physics interaction, thereby increase by two compatibility between components, the transparency, thermal characteristics and the mechanical property of hybrid film are improved comprehensively.
Purpose of the present invention is realized that by following technical measures wherein said composition of raw materials component is parts by weight except that specified otherwise.
A kind of preparation method of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film.
A. the preparation of lateral hydroxyl group containing polyamic acid
1～300 part of aromatic diamine of hydroxyl and the aromatic diamine that contains flexible bridge joint group are added in 10～10000 parts of solvents for 0～300 part; under nitrogen protection, stirred 0.5～1 hour; make the diamine dissolving; add 1～800 part of aromatic tetracarboxylic acid dianhydride again; stirring reaction is 10～20 hours in temperature-5～5 ℃ ice bath, makes faint yellow polyamic acid solution.
B. the preparation of lateral hydroxyl group containing polyimide amine
In above-mentioned polyamic acid solution, add 1～3000 part of dimethylbenzene, slowly be warming up to 160 ℃, reacted 2～4 hours, the water that produces in the closed loop procedure is by the backflow of dimethylbenzene, tell from water trap, precipitating in the product impouring methyl alcohol, and with little methyl alcohol extracting 1～2 time of boiling, under the negative pressure of 0.07～0.09atm, slough methyl alcohol, make the polyimide of lateral hydroxyl group containing.
C. the preparation of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film
Lateral hydroxyl group containing polyamic acid or polyimide are dissolved in the solvent for 1～1400 part, be made into mass percent concentration and be 5～15% solution, add 0～250 part of silane coupling agent that contains epoxy group(ing), in the presence of 0.1～10 part of catalyzer, in 120～150 ℃ of reactions of temperature 2～4 hours, be cooled to room temperature, add 1～1000 part of positive silicon ester again, stirred 6～24 hours, adopt the casting method film forming, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour, and obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film for 300 ℃.
Wherein, the aromatic diamine compound of lateral hydroxyl group containing is 2,4-two amido phenol, 4,4 '-two amidos-4, and " hydroxyl triphenyl methane and/or 1, phenoxy group-the 2-propyl alcohol is at least a for 3-two (4-amido).
The aromatic diamine that contains flexible bridge joint group is 4,4 '-diamines yl diphenyl ether, and triphen two ether diamines and/or 4,4 '-two amido ditanes are at least a.
The aromatic tetracarboxylic acid dianhydride is the phenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride and/or pyromellitic acid anhydride are at least a.
Positive silicon ester is a tetraethoxysilane, and tetramethoxy-silicane and/or butyl silicate are at least a.
The silane coupling agent that contains epoxy group(ing) is a glycidoxy-propyltrimethoxy silane, and epoxypropoxy methyl dimethoxysilane and/or epoxypropoxy triethoxyl silane are at least a.
Catalyzer is triethylamine, pyridine, diacetyl oxide, hydrochloric acid, N, and N-dimethyl benzylamine, sodium hydroxide, sodium ethylate and/or miaow Cuo are at least a.
Solvent is dimethylbenzene, N-Methyl pyrrolidone, N,N-dimethylacetamide, methyl alcohol and/or N, and dinethylformamide is at least a.
Experimental result shows, polyimide/silicon dioxide hybrid film by present method preparation all is transparent or semitransparent shape, its second-order transition temperature is 230～300 ℃, initial decomposition temperature (5% weightlessness) is 420～560 ℃, its good mechanical performance, tensile strength is 120～200MPa, and Young's modulus is 2.5～5.0Gpa, and the linear expansivity of hybrid film is 20～50ppm/k.
The present invention has following advantage:
1. when preparing lateral hydroxyl group containing polyimide amine, with the polyamic acid of known hydroxyl diamine and the synthetic lateral hydroxyl group containing of aromatic dianhydride, the structure of resulting polymkeric substance and the polymerization degree are known; And the introducing of lateral hydroxyl group does not influence the formation of polyamic acid and polyimide, so can prepare high-molecular weight, the flexible and changeable lateral hydroxyl group containing polyimide amine of backbone structure; In addition, the handiness height of hydroxyl diamine molecular designing can prepare the polyimide/silicon dioxide hybrid material that contains the new polymers structure that is difficult for realization with other method.
2. after introducing hydroxyl on the polyimide side chain, can by lateral hydroxyl group and the silane coupling agent that contains epoxy group(ing) be reflected at introduce on the polyimide molecule chain can with the side chain of inorganic precursors generation cohydrolysis, also can be by the silicon hydroxyl copolycondensation of lateral hydroxyl group and inorganic precursors hydrolysis generation, prepare existing stronger physics interaction between two components, the hybrid material that has chemical bond to link to each other again through sol gel reaction then.
3. by controlling kind and the density and the dosage of silane coupling agent of lateral hydroxyl group, the size of inorganic particle in the control hybrid material and the purpose of distribution thereof have been reached, thereby can prepare micron order even nano level hybrid material as required, significant to the development and application of instructing novel hybride materials.
4. the build-in attribute that had both kept the polyimide main chain by the SIDE CHAIN'S FUNCTIONALIZATION OF POLYIMIDE method, organic and interaction inorganic component are strengthened greatly, the hybrid film that obtains has high thermostability, its second-order transition temperature is 230～300 ℃, and initial decomposition temperature (5% weightlessness) is 420～560 ℃.
5. when dioxide-containing silica was 8～16%, hybrid film all was transparent or semitransparent shape, compared with pure Kapton, and the tensile strength of hybrid film has improved more than 30%; Its Young's modulus improves more than 25%.In addition, the dimensional stability of hybrid film improves more than 20%.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further detailed; can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment
1. with 274 grams 1; 3-two (4-amido) phenoxy group-2-propyl alcohol joins in an amount of N-Methyl pyrrolidone; stirring makes it dissolving; add 220 gram pyromellitic acid anhydrides again; the mass percent concentration of control solution is about 6%, and nitrogen protection was stirred 10 hours in-5～0 ℃ ice bath; obtain light yellow thick liquid, be the polyamic acid solution that contains pure lateral hydroxyl group.
In above-mentioned lateral hydroxyl group containing polyamic acid is molten, add 23.6 gram glycidoxy-propyltrimethoxy silanes and 1 gram N, the N-dimethyl benzylamine, reacted 4 hours down in 120 ℃, be cooled to room temperature, add 250 gram tetraethoxysilanes again, stirred 6 hours, the employing casting method is filmed, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour, and obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film for 300 ℃.
Lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film through this path of preparing is light yellow, and outward appearance is even, transparent.Its second-order transition temperature is 235 ℃; 5% heat decomposition temperature is 425 ℃; Its tensile strength is 123MPa, has improved 31% than Kapton itself; Its Young's modulus is 2.3Gpa, has improved 28% than Kapton itself.
2. with 37 grams 2; 4-two amido phenol and 140 grams 4; 4 '-diamines yl diphenyl ether joins in the reaction flask, with an amount of N,N-dimethylacetamide dissolving; add 310 gram phenyl ether tetracarboxylic dianhydrides again; the mass percent concentration of control solution is about 12%, and nitrogen protection was stirred 10 hours in 0～5 ℃ ice bath; obtain light yellow thick liquid, be the polyamic acid solution that contains the phenol lateral hydroxyl group.In polyamic acid solution, add 350 gram dimethylbenzene then, and be warming up to 160 ℃, reacted about 2 hours, the water that produces in the closed loop procedure is told from water trap by the backflow of dimethylbenzene, the cyclisation rate is calculated by the water of telling, after the cyclisation rate was greater than 85%, the product precipitating was in methyl alcohol, and with little methyl alcohol extracting 2 times of boiling, vacuum is sloughed methyl alcohol, gets lateral hydroxyl group containing polyimide amine.
Lateral hydroxyl group containing polyimide amine 487 grams are dissolved in N, be made into mass percent concentration in the N-N,N-DIMETHYLACETAMIDE and be about 10% solution, add 47 gram epoxypropoxy triethoxyl silanes and 1.5 gram pyridines, reacted 4 hours down for 120 ℃ in temperature, be chilled to room temperature, add 273 gram tetramethoxy-silicanes again, stirred 24 hours, and used the casting method film forming then, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour, and obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film for 300 ℃.
Lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film through this path of preparing is light yellow, and outward appearance is even, transparent.Its second-order transition temperature is 260 ℃; 5% heat decomposition temperature is 550 ℃; Its linear expansivity is 42ppm/k, has descended 29% than Kapton; Its tensile strength is 148MPa, has improved 78% than Kapton itself.
3. prescription and the technology by embodiment 2 makes lateral hydroxyl group containing polyimide amine.Then, lateral hydroxyl group containing polyimide amine 487 grams are dissolved in N, be made into mass percent concentration in the dinethylformamide and be about 10% solution, add the 1 gram 20%HCl aqueous solution and 546 gram tetraethoxysilanes, stirred 24 hours, use the casting method film forming then, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour, and obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film for 300 ℃.
Lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film through this path of preparing is light yellow, and outward appearance is even, transparent.Its second-order transition temperature is 255 ℃; 5% heat decomposition temperature is 551 ℃; Its tensile strength is 140MPa, has improved 69% than Kapton itself.
4. with 58 grams 4; 4 '-two amidos-4 " hydroxyl triphenyl methane and 160 grams 4; 4 '-two amido ditanes join in the reaction flask; with an amount of N-Methyl pyrrolidone dissolving, add 322 gram benzophenone tetracarboxylic dianhydride again, the mass percent concentration of control solution is about 10%; nitrogen protection; stirred 10 hours in-5～0 ℃ ice bath, obtain light yellow thick liquid, be the polyamic acid solution that contains the phenol lateral hydroxyl group.In polyamic acid solution, add 370 gram dimethylbenzene then, and be warming up to 160 ℃, reacted about 2 hours, the water that produces in the closed loop procedure is told from water trap by the backflow of dimethylbenzene, the cyclisation rate is calculated by the water of telling, after the cyclisation rate was greater than 85%, the product precipitating was in methyl alcohol, and with little methyl alcohol extracting 2 times of boiling, vacuum is sloughed methyl alcohol, gets lateral hydroxyl group containing polyimide amine.
Lateral hydroxyl group containing polyimide amine 500 grams are dissolved in the N-Methyl pyrrolidone, be made into mass percent concentration and be about 10% solution, add 47 gram glycidoxy-propyltrimethoxy silanes and 1.5 gram triethylamines, reacted 4 hours down in 120 ℃, be cooled to room temperature, add 357 gram tetraethoxysilanes again, stirred 24 hours, and used the casting method film forming then, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour, and obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film for 300 ℃.
Lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film through this path of preparing is light red, and outward appearance is even, transparent.Its tensile strength is 162MPa, has improved 78% than Kapton itself; Its Young's modulus is 3.2Gpa, has improved 60% than Kapton itself.
Claims (5)
1. the preparation method of a lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film is characterized in that:
A. the preparation of lateral hydroxyl group containing polyamic acid
1～300 part of aromatic diamine of hydroxyl and the aromatic diamine that contains flexible bridge joint group are added in 1～10000 part of solvent for 0～300 part; under nitrogen protection, stirred 0.5～1 hour; make the diamine dissolving; add 1～800 part of aromatic tetracarboxylic acid dianhydride again; stirring reaction is 10～20 hours in temperature-5～5 ℃ ice bath; make faint yellow polyamic acid solution
B. the preparation of lateral hydroxyl group containing polyimide amine
In above-mentioned polyamic acid solution, add 1～3000 part of dimethylbenzene, slowly be warming up to 160 ℃, reacted 2～4 hours, the water that produces in the closed loop procedure is told from water trap by the backflow of dimethylbenzene, precipitating in the product impouring methyl alcohol, and with little methyl alcohol extracting 1～2 time of boiling, under the negative pressure of 0.07～0.09atm, slough methyl alcohol, make the polyimide of lateral hydroxyl group containing
C. the preparation of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film
Lateral hydroxyl group containing polyamic acid or polyimide are dissolved in the solvent for 1～1400 part, be made into mass percent concentration and be 5～15% solution, add 0～250 part of silane coupling agent that contains epoxy group(ing), in the presence of 0.1～10 part of catalyzer, in 120～150 ℃ of reactions of temperature 2～4 hours, be cooled to room temperature, add 1～1000 part of positive silicon ester again, stirred 6～24 hours, adopt the casting method film forming, under the negative pressure of 0.09～0.1atm, handled 12 hours for 60 ℃ in temperature, handled 2 hours for 160 ℃, handled 2 hours for 200 ℃, handled 1 hour for 260 ℃, handled 0.5 hour for 300 ℃, obtained lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film
Wherein, the aromatic diamine compound of lateral hydroxyl group containing is two amido phenol, 4,4 '-two amidos-4 " hydroxyl triphenyl methane and/or 1; 3-two (4-amido) phenoxy group-2-propyl alcohol; the aromatic diamine that contains flexible bridge joint group is 4; 4 '-diamines yl diphenyl ether, triphen two ether diamines and/or 4,4 '-two amido ditanes, the aromatic tetracarboxylic acid dianhydride is phenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and/or pyromellitic acid anhydride.
2. according to the preparation method of the described a kind of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film of claim 1, it is characterized in that positive silicon ester is a tetraethoxysilane, tetramethoxy-silicane and/or butyl silicate are at least a.
3. according to the preparation method of the described a kind of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film of claim 1, the silane coupling agent that it is characterized in that containing epoxy group(ing) is that glycidoxy-propyltrimethoxy silane, epoxypropoxy methyl dimethoxysilane and/or epoxypropoxy triethoxyl silane are at least a.
4. according to the preparation method of the described a kind of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film of claim 1, it is characterized in that catalyzer is triethylamine, pyridine, diacetyl oxide, hydrochloric acid, N, N-dimethyl benzylamine, sodium hydroxide, sodium ethylate and/or miaow Cuo are at least a.
5. according to the preparation method of the described a kind of lateral hydroxyl group containing polyimide amine/SiO 2 hybrid film of claim 1, it is characterized in that solvent is dimethylbenzene, N-Methyl pyrrolidone, N,N-dimethylacetamide, methyl alcohol and/or N, dinethylformamide is at least a.
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| CN1218999C (en) | 2005-09-14 |
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