CN102650080A - Polyimide fiber spinning solution based on 3,3'-diamido-4,4'-dihydroxybiphenyl and preparation method thereof - Google Patents
Polyimide fiber spinning solution based on 3,3'-diamido-4,4'-dihydroxybiphenyl and preparation method thereof Download PDFInfo
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- CN102650080A CN102650080A CN2012101295078A CN201210129507A CN102650080A CN 102650080 A CN102650080 A CN 102650080A CN 2012101295078 A CN2012101295078 A CN 2012101295078A CN 201210129507 A CN201210129507 A CN 201210129507A CN 102650080 A CN102650080 A CN 102650080A
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Abstract
The invention relates to polyimide fiber spinning solution based on 3,3'-diamido-4,4'-dihydroxybiphenyl and a preparation method thereof. The structural formula of the compositions of the spinning solution is as follows. The preparation method comprises the following steps: under room temperature, 3,3'-diamido-4,4'-dihydroxybiphenyl and strong-polarity non-protonic organic solvent are added to a reactor to be stirred and dissolved, 3,3',4,4'-tetracarboxylicdiphenyl dianhydride is added to the reactor, the mixture in the reactor is stirred and subjected to reaction for 0.5-1 hour, and then 2,6-di (4-amino phenoxy) cyanobenzene is added, the mixture in the reactor is stirred and subjected to reaction for 3-5 hours, so the spinning solution is obtained. According to the raw materials adopted by the invention, the molecular weight of resin is easy to control, the molecular structure is easy to adjust, the preparation on polyimide high-performance fiber with ideal performance is facilitated, and the application prospect is good; according to the preparation method, the reaction conditions are mild, and the industrialization of products is facilitated.
Description
Technical field
The invention belongs to polyimide fiber spinning solution and preparation field thereof, particularly a kind of based on 3,3 '-diaminourea-4, polyimide fiber spinning solution of 4 '-dihydroxybiphenyl and preparation method thereof.
Background technology
Polyimides is the very excellent macromolecular material of one type of combination property; Have excellent especially heat resistance, lower temperature resistance, anti-flammability, electric property and mechanical property, be widely used in high-tech areas such as electronics microelectronics, Aero-Space, laser, photoelectricity.
The existing many reports of the research and development in relevant polyimide resin field:
Chinese invention patent CN101003716A discloses a kind of preparation method of phenolic hydroxy group polyimide adhesive; Be primarily characterized in that: (1) mol ratio is that 1: 1 mixture and the aromatic dicarboxylic acid anhydride of phenolic hydroxy group aromatic dicarboxylic amines or itself and other fragrance group diamine is in polar non-proton organic solvent by force; In 0 ℃～10 ℃ down reactions after 4～8 hours, obtain the polyhydroxyamide acid solution of homogeneous phase, transparent, thickness; (2) in the nitrogen atmosphere, add azeotropy dehydrant, heating; 120 ℃～160 ℃ of backflow azeotropic dehydrations imidization 1～6 hour; Be cooled to room temperature, obtained the phenolic hydroxy group polyimide adhesive, wherein azeotropy dehydrant is 1: 1～5 with the volume ratio of strong polar non-proton organic solvent.
Chinese invention patent CN1927908A discloses a kind of preparation method of phenolic hydroxy group polyimide powder; Be primarily characterized in that: (1) mol ratio is that 1: 1 mixture and the aromatic dicarboxylic acid anhydride of phenolic hydroxy group aromatic dicarboxylic amines or phenolic hydroxy group aromatic diamine and other diamine is in strong polar non-proton organic solvent; Under the nitrogen protection; After reacting 3～12 hours under 0 ℃～30 ℃; Obtain the polyhydroxyamide acid solution of transparent thickness, wherein, the mass percent that strong polar non-proton organic solvent accounts for whole reaction system is 5%～30%; (2) in the nitrogen atmosphere, add azeotropy dehydrant, heat temperature raising; In 120 ℃～160 ℃ temperature range, backflow azeotropic dehydration imidization 5～18 hours is cooled to room temperature; Filter washing, vacuumize; Obtain the phenolic hydroxy group polyimide powder, wherein, azeotropy dehydrant is 0.1～10: 1 with the volume ratio of strong polar non-proton organic solvent.
People such as the Yu Xinhai [development of high-temperature resistant single-component epoxy adhesive; Bonding, 2008,29 (12): 16-19] a kind of preparation method of polyimides is disclosed; Be primarily characterized in that: with maleic anhydride (MA) is end-capping reagent; With 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas (BAHPFP), 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] propane (BAPOPP), 2 of 2-; Two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides (BPADA) of 2-are the synthetic polyetherimide resin (HPEI) that has obtained phenolic hydroxy group of main material.
Chinese invention patent CN101560298A discloses a kind of thermoplastic fluorine-containing fully aromatic polyimide powder and preparation method thereof; Principal character is; Under the effect of catalyst, mol ratio is that 1: 0.8～1.2 fluorinated aromatic binary primary amine and aromatic dicarboxylic anhydride are in phenol solvent, with 100 ℃～180 ℃ temperature range internal reaction after 5-10 hour; Pour into while hot in the precipitating agent under the high-speed stirred state; Separate out pressed powder, filtration, washing, immersion, filtration, drying obtain thermoplastic fluorine-containing fully aromatic polyimide powder.
Chinese invention patent CN101580637A discloses a kind of alicyclic-containing polyimide film and preparation method thereof; Principal character is: under the room temperature, alicyclic ring binary primary amine, aromatic dicarboxylic primary amine are dissolved in the strong polar non-proton organic solvent, after stirring is homogeneous phase solution; Add aromatic dicarboxylic anhydride; Stir, in reaction under the room temperature after 1-3 hour, obtain homogeneous phase, transparent, the thick alicyclic ring polyamic acid resin solution that contains; Regulate the above-mentioned viscosity that contains alicyclic ring polyamic acid resin solution with strong polar non-proton organic solvent, film forming in casting machine, heat temperature raising carries out the dehydration fever imidization, cooling, demoulding, the alicyclic-containing polyimide film of acquisition homogeneous phase transparent.
Chinese invention patent CN101597428A discloses a kind of full aromatic fluorine containing transparent polyimide film and preparation method thereof, and principal character is: fluorinated aromatic binary primary amine and strong polar non-proton organic solvent are added in the polymerization bottle, stir under the room temperature; Fully after the dissolving; Ice-water bath is cooled to below 5 ℃, adds aromatic dicarboxylic anhydride, stirs; In 5 ℃-10 ℃ temperature range internal reactions after 3 hours, obtain homogeneous phase, transparent, thick fluorinated aromatic polyamic acid resin solution; With the viscosity that strong polar non-proton organic solvent is regulated above-mentioned fluorinated aromatic polyamic acid resin solution, film forming in casting machine, heat temperature raising carries out the dehydration fever imidization, cooling, demoulding obtains full aromatic fluorine containing transparent polyimide film.
Chinese invention patent CN101585923A discloses a kind of polyimide film with high visible light permeability and preparation method thereof; Principal character is: at room temperature, binary primary amine is dissolved in the strong polar non-proton organic solvent system, ice-water bath is cooled in 5 ℃-10 ℃ the temperature range; Add aromatic dicarboxylic anhydride; Stir, in 5 ℃-10 ℃ temperature range internal reactions after 4-10 hour, obtain homogeneous phase, transparent, thick polyamic acid resin solution; Regulate the viscosity of this polyamic acid resin solution, film forming in casting machine, hot imidization, the Kapton of acquisition homogeneous phase transparent.
Polyimides (PI) fiber is one of high-performance fiber that has higher-strength and modulus, good heat resistance, radiation resistance and electrical insulation capability; Particularly radiation hardness, electrical insulation capability are more more excellent than other high-performance fiber; Therefore can be widely used under some particular surroundings; Fields such as for example, fire-fighting, electronics, Aero-Space and war industry.The PI fiber once had extensive studies at home and abroad, but owing to reasons such as cost and technology, present industrialized PI fiber species seldom.
A kind of special polyimides fire resistance fibre that France Rhone-Poulenc company releases, model is 235AGF, the performance of this fiber mainly be do not fire, molten, do not form particulate, be heated and do not shrink.It has very strong powerful, acidproof, the organic solvent-resistant of machinery.Can be widely used as materials such as security blanket, seat protective cover, protective clothing, high temperature filtration.
P84 is a commercialization polyimide fiber the earliest; It is the product that Austrian Lenzing AG company (being present Inspec Fibers) releases in the mid-80; Be by 3,3 ', 4; 4 '-tetracarboxylic benzophenone dianhydride (BTDA) and 4,4 '--vulcabond diphenyl-methane (MDI) and toluene di-isocyanate(TDI) (TDI) make.
Developed countries such as the U.S., Russia are all stepping up to study polyimide fiber at present; Because the polyimide fiber of high-strength and high-modulus belongs to the reinforcing agent of advanced composite material; Be used for the manufacturing of Aeronautics and Astronautics device and rocket; Relevant report is fewer, but developed country never interrupted the research of this fiber.
People such as Yu Xinhai [Chinese invention patent CN101922061A] disclose a kind of polyimide fiber and preparation method thereof; Be primarily characterized in that: adopting mol ratio is that 1: 1 aromatic dicarboxylic primary amine and aromatic dicarboxylic anhydride is in polar non-proton organic solvent system by force; After stirring reaction 2-4 under the room temperature hour; Obtain the thick polyamic acid solution of homogeneous phase transparent; Wherein, the aromatic dicarboxylic primary amine is made up of the aromatic dicarboxylic primary amine of phenolic hydroxy group and the aromatic dicarboxylic primary amine of no phenolic hydroxyl group, and its mol ratio is 1: 0.1-10; Then, above-mentioned polyamic acid solution is poured in the spinning machine, screw rod is extruded, and through spinnerets, coagulating bath, becomes fine, stretches, and reels, and obtains as-spun fibre; At last, with this as-spun fibre high-temperature process, obtain the good polyimide fiber of combination property.
Summary of the invention
Technical problem to be solved by this invention provides a kind of based on 3; 3 '-diaminourea-4, polyimide fiber spinning solution of 4 '-dihydroxybiphenyl and preparation method thereof, the raw material of employing; The molecular resin amount is controlled easily; Molecular structure is adjustment easily also, helps preparing the polyimides high-performance fiber of ideal performance, has a good application prospect; Preparation method's reaction condition is gentle, helps the industrialization of product.
Of the present invention a kind of based on 3,3 '-diaminourea-4, the polyimide fiber spinning solution of 4 '-dihydroxybiphenyl, the structural formula of the component of said spinning solution is following:
Of the present invention a kind of based on 3,3 '-diaminourea-4, the polyimide fiber preparation method of spinning dope of 4 '-dihydroxybiphenyl comprises:
At room temperature, with 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl adds in the agitated reactor with strong polar non-proton organic solvent; After the stirring and dissolving, add 3,3 ', 4; 4 '-tetracarboxylic biphenyl dianhydride stirring reaction 0.5-1 hour, adds 2, two (4-amino-benzene oxygen) benzonitriles of 6-again; Stirring reaction 3-5 hour, obtain the homogeneous phase thickness based on 3,3 '-diaminourea-4, the polyimide fiber spinning solution of 4 '-dihydroxybiphenyl;
Wherein, 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl and 2, the mol ratio of two (4-amino-benzene oxygen) benzonitriles of 6-is 1: 1; 3,3 ', 4, the molal quantity of 4 '-tetracarboxylic biphenyl dianhydride equals 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl and 2, the molal quantity of two (4-amino-benzene oxygen) benzonitriles of 6-it; Strong polar non-proton organic solvent is 3 milliliters-4 milliliters with the volume mass ratio of total reactant: 1 gram, and the quality of total reactant is meant 3,3 '-diaminourea-4; 4 '-dihydroxybiphenyl, 2, two (4-amino-benzene oxygen) benzonitriles and 3 of 6-, 3 '; 4, the quality sum of 4 '-tetracarboxylic biphenyl dianhydride.
Described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, DMAC N,N, N-ethyl-2-pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
Beneficial effect
(1) raw material of the present invention's employing, the molecular resin amount is controlled easily, and molecular structure is adjustment easily also, helps preparing the polyimides high-performance fiber of ideal performance, has a good application prospect;
(2) preparation method's reaction condition of the present invention is gentle, and course of reaction is carried out under normal pressure, and is simple to operate; The reaction raw materials convenient sources, cost is low, does not relate to also not producing corrosive substance, and organic solvent uses the few and easy recovery of kind, and Recycling repeatedly is environmentally friendly; The used synthesis technique equipment of preparation process is universal, can utilize the complete set of equipments of existing production polyimide resin to come embodiment of the present invention fully, is very beneficial for the industrialization of product.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
At room temperature, with 21.6 gram (0.1 moles) 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl and 390 milliliters of N-N-methyl-2-2-pyrrolidone N-s add in the agitated reactor; After the stirring and dissolving, add 58.8 gram (0.2 moles) 3,3 '; 4,4 '-tetracarboxylic biphenyl dianhydride powder, stirring reaction 0.5 hour; Add 31.7 gram (0.1 moles) 2 again, two (4-amino-benzene oxygen) benzonitriles of 6-, stirring reaction 3 hours; Obtain a kind of of homogeneous phase thickness, 3 '-diaminourea-4, the polyimide fiber spinning solution of 4 '-dihydroxybiphenyl based on 3.
Utilize its viscosity of 80 ℃ of CAP2000+ vertebral plate viscosity instrumentation of BROOKFIELD to be 3540mPa.s.
Get an amount of above-mentioned polyimide fiber spinning solution, be coated on equably on the clean flat glass film, put into air blast high temperature oven film-forming, concrete technology is: be warming up to 120 ℃ from room temperature, kept 30 minutes; Continue to be warming up to 180 ℃, kept 30 minutes; Continue to be warming up to 280 ℃, kept 30 minutes, stop heating, naturally cool to room temperature, the poach demoulding, drying obtains Kapton.Utilize electronic tensile machine to survey its mechanical property, tensile strength is 130.2MPa, and elongation at break is 32.3%.
Above-mentioned polyimide fiber spinning solution is poured in the spinning machine, and screw rod is extruded, and is 1: 10 N through spinnerets, volume ratio; The mixed liquor coagulating bath of N-dimethylacetylamide and ethanol becomes fine, stretches; Reel, obtain as-spun fibre, through the gradient high-temperature process in 150 ℃ of-350 ℃ of temperature ranges; Obtain based on 33 '-diaminourea-4, the polyimide fiber of 4 '-dihydroxybiphenyl.
Claims (3)
1. one kind based on 3,3 '-diaminourea-4, and the polyimide fiber spinning solution of 4 '-dihydroxybiphenyl is characterized in that: the structural formula of the component of said spinning solution is following:
2. one kind based on 3,3 '-diaminourea-4, and the polyimide fiber preparation method of spinning dope of 4 '-dihydroxybiphenyl comprises:
At room temperature, with 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl adds in the agitated reactor with strong polar non-proton organic solvent; After the stirring and dissolving, add 3,3 ', 4; 4 '-tetracarboxylic biphenyl dianhydride stirring reaction 0.5-1 hour, adds 2, two (4-amino-benzene oxygen) benzonitriles of 6-again; Stirring reaction 3-5 hour, obtain the homogeneous phase thickness based on 3,3 '-diaminourea-4, the polyimide fiber spinning solution of 4 '-dihydroxybiphenyl;
Wherein, 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl and 2, the mol ratio of two (4-amino-benzene oxygen) benzonitriles of 6-is 1: 1; 3,3 ', 4, the molal quantity of 4 '-tetracarboxylic biphenyl dianhydride equals 3,3 '-diaminourea-4,4 '-dihydroxybiphenyl and 2, the molal quantity of two (4-amino-benzene oxygen) benzonitriles of 6-it; Strong polar non-proton organic solvent is 3 milliliters-4 milliliters with the volume mass ratio of total reactant: 1 gram, and the quality of total reactant is meant 3,3 '-diaminourea-4; 4 '-dihydroxybiphenyl, 2, two (4-amino-benzene oxygen) benzonitriles and 3 of 6-, 3 '; 4, the quality sum of 4 '-tetracarboxylic biphenyl dianhydride.
3. according to claim 2 a kind of based on 3; 3 '-diaminourea-4; The polyimide fiber preparation method of spinning dope of 4 '-dihydroxybiphenyl; It is characterized in that: described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, DMAC N,N, N-ethyl-2-pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, the dimethyl sulfoxide (DMSO).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679571A (en) * | 2018-12-21 | 2019-04-26 | 东华大学 | A kind of DADHBP type silicon-containing adhesive and preparation method thereof |
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| JPS5516925A (en) * | 1978-07-19 | 1980-02-06 | Inst Buisokomorekuriyarunihi S | Production of polyimide fiber |
| CN1821457A (en) * | 2006-03-17 | 2006-08-23 | 东华大学 | Polyimide fiber and its preparing method |
| CN101003716A (en) * | 2007-01-19 | 2007-07-25 | 东华大学 | Method for preparing binder of polyimide of containing phenolic hydroxyl group |
| CN101392059A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Colorless transparent aromatic polyimide film and preparation method thereof |
| CN101423609A (en) * | 2008-10-21 | 2009-05-06 | 东华大学 | Method for preparing polyimide powder containing active ethylene group |
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- 2012-04-27 CN CN201210129507.8A patent/CN102650080B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516925A (en) * | 1978-07-19 | 1980-02-06 | Inst Buisokomorekuriyarunihi S | Production of polyimide fiber |
| CN1821457A (en) * | 2006-03-17 | 2006-08-23 | 东华大学 | Polyimide fiber and its preparing method |
| CN101003716A (en) * | 2007-01-19 | 2007-07-25 | 东华大学 | Method for preparing binder of polyimide of containing phenolic hydroxyl group |
| CN101423609A (en) * | 2008-10-21 | 2009-05-06 | 东华大学 | Method for preparing polyimide powder containing active ethylene group |
| CN101392059A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Colorless transparent aromatic polyimide film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679571A (en) * | 2018-12-21 | 2019-04-26 | 东华大学 | A kind of DADHBP type silicon-containing adhesive and preparation method thereof |
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