CN1563149A - Coupled reaction method for preparing nano hybridization material of polyimide-oxide of silicon - Google Patents
Coupled reaction method for preparing nano hybridization material of polyimide-oxide of silicon Download PDFInfo
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- CN1563149A CN1563149A CN 200410014554 CN200410014554A CN1563149A CN 1563149 A CN1563149 A CN 1563149A CN 200410014554 CN200410014554 CN 200410014554 CN 200410014554 A CN200410014554 A CN 200410014554A CN 1563149 A CN1563149 A CN 1563149A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 17
- 238000009396 hybridization Methods 0.000 title abstract description 5
- 238000005859 coupling reaction Methods 0.000 title description 3
- 229910052710 silicon Inorganic materials 0.000 title description 2
- 239000010703 silicon Substances 0.000 title description 2
- 239000004642 Polyimide Substances 0.000 claims abstract description 20
- 229920001721 polyimide Polymers 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 6
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- -1 diamino phenoxy sulfobenzide Chemical compound 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 claims description 4
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- BIXGISJFDUHZEB-UHFFFAOYSA-N 2-[9,9-bis(4-methylphenyl)fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC(C=3C=C4C(C5=CC=CC=C5C4=CC=3)(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=C2C2=CC=CC=C21 BIXGISJFDUHZEB-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- TWKVCLRLFUIZLG-UHFFFAOYSA-N 5-(4-carboxyphenyl)cyclohexa-2,4-diene-1,1,2-tricarboxylic acid Chemical compound C1C(C(O)=O)(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 TWKVCLRLFUIZLG-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- LDWBQADKOUWRIR-UHFFFAOYSA-N n-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)NC1=CC=CC=C1 LDWBQADKOUWRIR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000006358 imidation reaction Methods 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012412 chemical coupling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Abstract
In the preparation method, hydrolytic reaction of inorganic material precursor is supplied by dewatering between molecules in course of generating polyimide by cyclizing prepolymer-eurelon acid so polymerization reaction and sol reaction are coupled to finalize imidation and sol-gel reaction simultaneously for obtaining hybridization material of inorganic material-high dispersion inorganic phase polyimide.
Description
Technical field:
The present invention relates to a kind of preparation method of organic-inorganic nano hybrid material, especially relate to a kind of preparation method of polyimide-Si oxide nano-hybrid material.
Background technology:
Sol-gel method be meant metal the hydrolysis in solution (being generally organic solvent) of organic or inorganic compound, be condensed into sol solutions, remove solvent and/or heating then and change into gel, finally make the method for soild oxide or other solid chemical compound.Its distinctive chilling process provides possibility for the preparation organic/inorganic hybridization material.Organic/inorganic hybridization material mostly is nano hybridization, and promptly the disperse phase yardstick makes it compare with traditional matrix material and has more excellent comprehensive performance in nanometer scale.As: nano-hybrid material has optical transparence, and the organism of different performance and the introducing of inorganics have strengthened the over-all properties of material, as electrical property, mechanical property etc.
In numerous polymkeric substance, polyimide is widely studied and adopts because of its significant high thermal stability and good physical strength and chemical stability.The essence of sol-gel process is a kind of nucleophilic substitution process, and the Electron Affinities of silicon is low, and undersaturation is zero, so the reactive behavior of siloxanes is low relatively, its hydrolysis and polycondensation process are controlled easily.So synthetic tetraethoxysilane alkoxyl silicone alkanes raw materials such as (TEOS) that uses usually of hybrid inorganic-organic materials.
The polyimide for preparing at present-Si oxide hybrid material does not reach the performance of the hybrid material of expection far away.Tracing it to its cause, mainly is that the biphase consistency is too poor.Because biphase pattern and combination are related to the mechanical property and the dynamic properties of material,, research after this improves on the two-phase consistency so mainly concentrating on.The research that reduces the degree that is separated concentrates on following two aspects: one, the end group of functionalization organic oligomer or the inorganic precursor of organic replacement make organic-inorganic phase chemistry key joint.Reported of the work of the oligopolymer polyimide binding of their synthetic functionalizations as McGrath etc. to the collosol and gel network, they have made on the end of the chain band of PI amido, hybrid material two-phase with this oligopolymer preparation has good consistency (Mater.Res.Soc.Symp.Proc.1990,175,179).Ahmad etc. adopts the inorganic precursor APTMOS of organic replacement for another example and since anilino can with the carboxyl binding of organic moiety, so the combination degree of organic-inorganic is very high, the degree of being separated (1. Chem.Mater.1994,6,943. 2. Macromol.Rep.1994 have been reduced, A31,411).Two, introduce chemical coupling agent.Coupling agent be class two ends have can with the chemical functional group's of inorganic organic moiety binding material.Reported as Mascia etc. and to have adopted GPTMOS and ICTMOS coupling polyamic acid on the network structure of Si oxide, and then carry out polycondensation, two-phase still has compatible preferably (J.Mater.Sci.Lett.1994,13,641) when silicone content reaches higher value.
Reduce molecular weight owing to hydrolysis easily takes place polyamic acid in the presence of water, sol-gel process and organic polycondensation process are carried out in an individual system in above-mentioned each method, that is to say that the required aqueous solution of sol-gel process provides the condition of degraded polyamic acid.And the reduction of the preceding polymer molecular amount of polyimide will directly influence the mechanical property and the thermal characteristics of material.So there is very big drawback in traditional improving one's methods.
Morikawa etc. obtain the salt of triethylamine with polyamic acid and triethylamine effect, are that solvent carries out the sol-gel reaction with methyl alcohol, and the morphological structure of hybridized film and the size that is separated all are greatly improved, and can obtain containing 20%SiO
2Transparent film (1. J.Mater, Chem., 2,679,1992; 2. Chem.Mater., 6,913,1994).But this method, synthesis step is more loaded down with trivial details, and the noxious solvent amount of use is many, is difficult for being adopted by industrialization.
GING-HO HSIUE etc. has studied the problem of the Prepared by Sol Gel Method hybrid material of anhydrous solution, they have adopted the alkoxide of the phenyl replacement with autocatalysis hydrolysis as inorganic precursor, avoided in system, introducing water molecules, kept material favorable mechanical performance, and when bringing up to 45%, silicone content still has an optical transparence (J.Applied Polymer Science, 76,1609).The defective of this method is, inorganicly only reaches certain dispersity by last mechanical blending with organic phase, and preparation cycle is long, the step complexity, and required quantity of solvent is big.
Summary of the invention:
The purpose of this invention is to provide a kind of preparation cycle weak point, have the synthetic method of favorable mechanical performance and thermal characteristics, the inorganic polyimide mutually of polymolecularity-Si oxide nano-hybrid material.
Technical solution of the present invention is: present method is equipped with on the basis of hybrid material in traditional sol-gel legal system, utilize second step in the two-step approach synthesis of polyimides process, be that its performed polymer-polyamic acid cyclisation generates intermolecular dehydration supply inorganics precursor hydrolysis reaction in the polyimide process, thereby polyreaction and colloidal sol reaction are coupled together, finish imidization and sol gel reaction simultaneously, polyimide-inorganics hybrid material to make the inorganic phase of polymolecularity the steps include:
(a) etc. the monomer diamines of mol ratio and dianhydride mixed in polar aprotic solvent 4-10 hour, the synthesizing polyamides acid solution;
(b) mixing solutions of 100: 1～10: 1 organoalkoxysilane of dropping volume percent, Glacial acetic acid or dilute hydrochloric acid in above-mentioned polyamic acid solution, wherein the amount of organoalkoxysilane is 2a/n～10a/n mol, a is the mole number of polyamic acid, n is the number of alkoxyl group in the organoalkoxysilane structural formula, drop rate is 0.1ml/min～2ml/min, drips the back and stirs 1～20 hour;
" alkyl or aromatic group n are the natural number of 1-4 to OR '-alkoxy base R
(c) thermal treatment is put into baking oven with above-mentioned solution and is heated, and temperature programming to 200 ℃～350 ℃ preferably is warmed up to 250 ℃～350 ℃.Obtain inorganic mutually finely dispersed polyimide-Si oxide hybrid material.Wherein the monomer diamines is an aromatic diamine, is preferably 4,4 '-diaminodiphenyl oxide (ODA), diamino phenoxy sulfobenzide (BAPS), 1, two (3-amino-benzene oxygen) benzene (BAPB) of 3-, diaminodiphenylsulfone(DDS) (DDS), diaminobenzophenone (DABP), methylene-dianiline (MDA), 1,3-two (3-amino-benzene oxygen) benzene (APB), perfluor isopropylidene diamine (BDAF), 2,2 '-two (4-amino) HFC-236fa (6FBA); Dianhydride is the aromatic series dianhydride, is preferably pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), oxygen support two phthalic anhydrides (ODPA), dihydroxyphenyl propane dianhydride (BPADA), benzophenone tetracarboxylic dianhydride (BTDA), 2,2 '-two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA); Organoalkoxysilane is methyl silicate (TMOS), tetraethoxy (TEOS), Union carbide A-162 (MTEOS), phenyl triethoxysilane (PTEOS), phenylamino trimethoxy silicon (APTMOS).Inorganic phase size has reached 50nm～1um order of magnitude.
Beneficial effect of the present invention is: utilized in the system of preparation hybrid material, there are two reactions simultaneously to the supply and demand of water molecules, the hydrolysis reaction that is sol-gel process needs feedwater, and the intermolecular cyclodehydration of polyamic acid is reflected at the molecule segment place water is provided, and this is for the distributed locations and the degree of scatter that need determine inorganic phase.Disperse inorganic method mutually to compare with the mechanical stirring that adopts in the routine preparation, improved the degree of scatter of inorganic phase greatly, improved two alternate consistencies.The present invention is coupled together organic polycondensation and solgel reaction that this supply and demand is provided just, has made the polyimide-Si oxide hybrid material of inorganic phase high dispersive.
Embodiment:
Embodiment 1.
The diamines yl diphenyl ether (ODA) and the 150mlN that in the Erlenmeyer flask of a cleaning, add 0.1mol, N '-dimethyl formamide (DMF) is stirred to dissolving fully, and equimolar pyromellitic acid anhydride (PMDA) adds in batches, stirring reaction 4-5 hour, generate the faint yellow polyamic acid solution of heavy-gravity.Drip the mixed solution of 20ml tetraethoxy (TEOS) and 2ml Glacial acetic acid again in above-mentioned solution while stirring, drop rate is 0.1-5ml/min, stirring reaction 1-2 hour.Polymers soln is put into baking oven, and temperature programming is heat-treated: 80 ℃ 2 hours, 170 ℃ 4 hours, 200 ℃ 2 hours, 280 ℃ 4 hours, finally obtain polyimide-silicon dioxide hybrid materials.
Embodiment 2.
Add 0.1mol diaminodiphenylsulfone(DDS) (DDS) and 150mlN-methyl-2-pyrrolidone (NMP) in the Erlenmeyer flask of a cleaning, be stirred to dissolving fully, the preparation method finally obtains SiO with embodiment 1
2Finely dispersed polyimide hybrid material.
Embodiment 3.
The diamines yl diphenyl ether (ODA) and the 150mlN that in the Erlenmeyer flask of a cleaning, add 0.1mol, N '-dimethyl formamide (DMF), be stirred to dissolving fully, add 3 of 0.1mol in batches, 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), stirring reaction 7-8 hour, generate the faint yellow polyamic acid solution of heavy-gravity.The mixed solution of Dropwise 5 0ml tetraethoxy (TEOS) and 2ml Glacial acetic acid while stirring in above-mentioned solution again, drop rate is 0.5 ~ 5 ℃/ml, stirring reaction 10-12 hour.Polymers soln is put into baking oven, and temperature programming is heat-treated: 80 ℃ 6 hours, 170 ℃ 2 hours, 200 ℃ 4 hours, 350 ℃ 4 hours, finally obtain the finely dispersed polyimide of inorganic particle-Si oxide hybrid material.
Embodiment 4.
In the Erlenmeyer flask of a cleaning, add 1 of 0.1mol, two (3-amino-benzene oxygen) benzene (BAPB) of 3-and 150ml N, N '-N,N-DIMETHYLACETAMIDE (DMA
C), be stirred to fully dissolving, add in three batches 0.1mol 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), stirring reaction 4～8 hours generates the faint yellow polyamic acid solution of heavy-gravity.Drip the mixed solution of 75ml tetraethoxy (TEOS) and 2ml Glacial acetic acid again in above-mentioned solution while stirring, drop rate is 1-5ml/min, stirring reaction 15-20 hour.Heat treating method is with embodiment 1.Obtain the finely dispersed polyimide of inorganic particle-Si oxide hybrid material.
Claims (8)
1. method for preparing polyimide-Si oxide nano-hybrid material, utilize the polyamic acid cyclisation to generate intermolecular dehydration supply organoalkoxysilane hydrolysis reaction in the polyimide process, thereby polyreaction and sol gel reaction are coupled together, finish imidization and sol gel reaction simultaneously, the steps include:
(a) etc. the monomer diamines of mol ratio and dianhydride mixed in polar aprotic solvent 4-10 hour, the synthesizing polyamides acid solution;
(b) mixing solutions of dropping 100: 1～10: 1 organoalkoxysilane of volume percent and Glacial acetic acid or dilute hydrochloric acid in above-mentioned polyamic acid solution, wherein the amount of organoalkoxysilane is 2a/n～10a/n mol, a is the mole number of polyamic acid, n is the number of alkoxyl group in the organoalkoxysilane structural formula, drop rate is 0.1ml/min～5ml/min, drips the back and stirs 1～20 hour;
" alkyl or aromatic group n are that the order of 1-4 is so counted to OR-alkoxy base R
(c) thermal treatment puts it into baking oven thermal treatment, and temperature programming to 200 ℃～350 ℃ obtains inorganic mutually finely dispersed polyimide-Si oxide hybrid material.
2. the preparation method of polyimide according to claim 1-Si oxide nano-hybrid material is characterized in that temperature programming to 250 ℃～350 ℃.
3. the preparation method of polyimide according to claim 1-Si oxide nano-hybrid material is characterized in that the monomer diamines is an aromatic diamine.
4. the preparation method of polyimide according to claim 3-Si oxide nano-hybrid material, it is characterized in that aromatic diamine is 4,4 '-diaminodiphenyl oxide (ODA), diamino phenoxy sulfobenzide (BAPS), 1, two (3-amino-benzene oxygen) benzene (BAPB) of 3-, diaminodiphenylsulfone(DDS) (DDS), diaminobenzophenone (DABP), methylene-dianiline (MDA), 1,3-two (3-amino-benzene oxygen) benzene (APB), perfluor isopropylidene diamine (BDAF), 2,2 '-two (4-amino) HFC-236fa (6FBA).
5. the preparation method of polyimide according to claim 1-Si oxide nano-hybrid material is characterized in that the monomer dianhydride is the aromatic series dianhydride.
6. the preparation method of polyimide according to claim 5-Si oxide nano-hybrid material is characterized in that the aromatic series dianhydride is pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), oxygen support two phthalic anhydrides (ODPA), dihydroxyphenyl propane dianhydride (BPADA), benzophenone tetracarboxylic dianhydride (BTDA), 2,2 '-two (3, the 4-dicarboxylic acid) hexafluoropropane dianhydride (6FDA).
7. the preparation method of polyimide according to claim 1-Si oxide nano-hybrid material, it is characterized in that organoalkoxysilane is methyl silicate (TMOS), tetraethoxy (TEOS), Union carbide A-162 (MTEOS), phenyl triethoxysilane (PTEOS), phenylamino trimethoxy silicon (APTMOS).
8. according to the preparation method of the described described polyimide of claim 1-Si oxide nano-hybrid material, it is characterized in that making polyimide-Si oxide hybrid material that inorganic phase size reaches 50nm～1um order of magnitude.
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| CN 200410014554 CN1252136C (en) | 2004-04-05 | 2004-04-05 | Coupled reaction method for preparing nano hybridization material of polyimide-oxide of silicon |
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| CN 200410014554 CN1252136C (en) | 2004-04-05 | 2004-04-05 | Coupled reaction method for preparing nano hybridization material of polyimide-oxide of silicon |
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| CN1563149A true CN1563149A (en) | 2005-01-12 |
| CN1252136C CN1252136C (en) | 2006-04-19 |
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| CN 200410014554 Expired - Lifetime CN1252136C (en) | 2004-04-05 | 2004-04-05 | Coupled reaction method for preparing nano hybridization material of polyimide-oxide of silicon |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407590B (en) * | 2008-11-27 | 2011-11-16 | 南京工业大学 | Preparation of high modulus, low thermal expansion coefficient polyimide hybridization film |
| CN103113587A (en) * | 2013-03-14 | 2013-05-22 | 华威聚酰亚胺有限责任公司 | Flexible hyperbranched semi-interpenetrating fluorinated polysiloxane polyimide film and preparation method thereof |
| CN103435826A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Method for preparing atomic oxygen resisting polyimide hybrid thin films by sol-gel method in anhydrous system |
| CN107237141A (en) * | 2017-05-08 | 2017-10-10 | 上海大学 | The preparation method that the hydrophobic polyimides that a kind of surface is modified is weaved cotton cloth |
| CN111533911A (en) * | 2020-05-14 | 2020-08-14 | 深圳大学 | Polyimide nano hybrid material and preparation method thereof |
| CN113265085A (en) * | 2021-04-29 | 2021-08-17 | 同济大学 | Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof |
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2004
- 2004-04-05 CN CN 200410014554 patent/CN1252136C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407590B (en) * | 2008-11-27 | 2011-11-16 | 南京工业大学 | Preparation of high modulus, low thermal expansion coefficient polyimide hybridization film |
| CN103113587A (en) * | 2013-03-14 | 2013-05-22 | 华威聚酰亚胺有限责任公司 | Flexible hyperbranched semi-interpenetrating fluorinated polysiloxane polyimide film and preparation method thereof |
| CN103435826A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Method for preparing atomic oxygen resisting polyimide hybrid thin films by sol-gel method in anhydrous system |
| CN107237141A (en) * | 2017-05-08 | 2017-10-10 | 上海大学 | The preparation method that the hydrophobic polyimides that a kind of surface is modified is weaved cotton cloth |
| CN107237141B (en) * | 2017-05-08 | 2019-10-11 | 上海大学 | A kind of preparation method for the hydrophobic polyimides woven fabric that surface is modified |
| CN111533911A (en) * | 2020-05-14 | 2020-08-14 | 深圳大学 | Polyimide nano hybrid material and preparation method thereof |
| CN113265085A (en) * | 2021-04-29 | 2021-08-17 | 同济大学 | Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof |
| CN113265085B (en) * | 2021-04-29 | 2022-06-21 | 同济大学 | Polymethylsilsesquioxane-polyimide composite aerogel material and preparation and application thereof |
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|---|---|
| CN1252136C (en) | 2006-04-19 |
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