CN101487190B - Polyimide carbon fiber sizing agent and method for producing the same - Google Patents
Polyimide carbon fiber sizing agent and method for producing the same Download PDFInfo
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- CN101487190B CN101487190B CN2009100462616A CN200910046261A CN101487190B CN 101487190 B CN101487190 B CN 101487190B CN 2009100462616 A CN2009100462616 A CN 2009100462616A CN 200910046261 A CN200910046261 A CN 200910046261A CN 101487190 B CN101487190 B CN 101487190B
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Abstract
The invention relates to a polyimide carbon fiber tackifier with the molecular general formula shown at the right part. The preparation method of the tackifier comprises the steps as follows: quaternary primary aromatic amines and single anhydride are dissolved in strong-polarity aprotic organic solvent by the molar ratio of 1:2, mixed for reaction for 0.5-2 hours at the temperature of 0-20 DEG C; subsequently, binary primary aromatic amines and 2, 2-bi (3-amido-4-(4-cyano phenoxy) phenyl) Hexafluoropropane are added, mixed, dissolved and cooled by icy water bath; subsequently, binary aromatic anhydride is added and mixed for reaction for 2-4 hours at the temperature of 0-20 DEG C; subsequently, acidic catalyst and entrainer are added; after the heating refluxing water-diversion reaction for 5-12 hours, the entrainer is collected for recovery and reusing and transparent and sticky polyimide solution with uniform phase is obtained; the polyimide carbon fiber tackifier has excellent dimension stability, mechanic property and heat resistance; furthermore, the reaction condition of the preparation method is moderate, the reaction raw material has convenient source and low cost and is friendly to the environment.
Description
Technical field
The invention belongs to carbon fiber sizing agent and preparation field thereof, particularly relate to a kind of polyimide carbon fiber sizing agent and preparation method thereof.
Background technology
Polyimide is the very excellent polymkeric substance of a class over-all properties, has very good thermotolerance, lower temperature resistance, solvent resistance, self lubricity and characteristic such as fire-retardant, simultaneously, also has very excellent mechanical property and dielectric properties.Therefore, it is widely used in photovoltaic material, nonlinear optical material; The high temperature material of spaceship, satellite or space craft etc.; The advanced configuration matrix material of aspects such as aerospace, automobile, electromechanics, C level or 200 higher level insulating materials, high-temperature resistance adhesive etc.; And interlayer dielectic, super large-scale integration passivating coating and the alpha-particle blocking layer coating material etc. of the body material of the FPC of electronics microelectronic or PCB, IC.
Resin transfer molding (RTM) process (RTM) is a kind of liquid molding technology.Because of it has low die cost, low organism volatile quantity, designability and is suitable in the moulding in batches advantage such as large-scale integral complex component, be widely used in a plurality of fields such as aerospace, shipbuilding, automobile, electronics and covil construction, and become the focus of composite technology research in recent years.
In the RTM technological process, the various strongtheners (body) of lay all are in no external force effect and under the separate state in the mold closing, its take place easily at matched moulds with when annotating people's resin slippage dislocation and (or) defective such as inner flexing, destroy shop layer by structure, mechanics requirement design, cause the unpredictable of composite product degradation and performance, especially complex-shaped goods.Therefore, the preform technology of preparing is worth furtheing investigate as a core technology in the RTM technology undoubtedly, and wherein the research of pre-setting agent then is the key of whole preform technology of preparing.
[setting agent is to the influence of composite materials property for people such as Liao Yongbo, New Chemical Materials, 2006,34 (10): 62-65] influence of setting agent content to 3186 satin weaves, 827 unidirectional carbon cloths/3266 polymer matrix composites flexural strengths, interlaminar shear strength and modulus disclosed.The result shows: influence rule, the setting agent optimum amount of composite materials property all has very strong dependency to the texture of strongthener during setting agent content; In 3186 satin weaves/3266 resin systems and 827 unidirectional carbon cloths/3266 resin systems, the setting agent consumption is respectively 8% and at 5% o'clock, and the adding of setting agent does not cause tangible deterioration effect to the mechanical property of matrix material.But do not disclose the molecular structure of setting agent, more do not have its preparation method.
Its cloud of crow sound of laughing people such as grade [warm setting agent and RTM precast body performance thereof in a kind of, material engineering, 2006, (3): 37-39,43] the mixing use properties of ES-T321 setting agent and paired RTM special epoxy resin 3266 thereof is disclosed, ES-T321 can be prepared into acetone soln or powder sizing material, and is easy to use; The fusing point of ES-T321 has the moving performance of flushing of anti-current preferably than the RTM injection temperature window height of 3266 resins, and the fabric that can guarantee to finalize the design is not broken up when resin injection; ES-T321 can be dissolved in the resin under the solidification value of 3266 resins, and with the reaction of 3266 solidifying agent; Add setting agent the thermal characteristics of mixed with resin system is not almost had influence; The spring-back effect of the preform that typing is handled is little, and the resilience of the preform of solution method typing is littler than powder method.Yet molecular structure of ES-T321 setting agent and preparation method thereof is also still unexposed.
At present, though in the Resins, epoxy RTM moulding process, relevant carbon fiber premolding is reported to some extent with the application of setting agent, and its molecular structure or preparation method be there is no open report; The carbon fiber premolding setting agent of relevant polyimide RTM moulding process is not seen open report yet.
Therefore, the present invention furthers investigate molecular structure of polyimide carbon fiber sizing agent and preparation method thereof.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polyimide carbon fiber sizing agent and preparation method thereof, and this polyimide carbon fiber sizing agent has excellent size stability, mechanical property and thermotolerance; And preparation method's reaction conditions gentleness, reaction process 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 corrosives, and organic solvent uses the few and easy recovery of kind, and Recycling repeatedly is environmentally friendly.
Chemical equation of the present invention is as follows:
Wherein, m, n, p are more than or equal to 1 and less than 20 natural number; Independent, uncorrelated mutually separately;
In the formula, the structural formula of single acid anhydride is:
Aromatic binary primary amine residue-Q
1-be:
Connection base-the Q of aromatic series quaternary primary amine
2-be:
Described aromatic dicarboxylic anhydride residue=Ar=is:
A kind of polyimide carbon fiber sizing agent of the present invention, its general formula of molecular structure is:
Wherein :-Q
1-be aromatic binary primary amine residue;=Ar=is the aromatic dicarboxylic anhydride residue;-Q
2The connection base of-aromatic series quaternary primary amine;-R-is single acid anhydride residue; M, n, p are more than or equal to 1, and less than 20 natural number, independent separately uncorrelated mutually;
Proterties: the thick solution of homogeneous phase transparent;
The molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent;
The molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent;
The molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent;
The preparation method of a kind of polyimide carbon fiber sizing agent of the present invention comprises:
Aromatic series quaternary primary amine and single acid anhydride were dissolved in strong polar non-proton organic solvent in 1: 2 in molar ratio, in 0 ℃-20 ℃ temperature range after stirring reaction 0.5-2 hour, add aromatic dicarboxylic primary amine and 2, two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, after the stirring and dissolving, the ice-water bath cooling, add aromatic dicarboxylic anhydride, stir, after 2-4 hour, add an acidic catalyst and entrainer in 0 ℃-20 ℃ temperature range internal reactions, reflux divides the water reaction after 5-12 hour, tell entrainer (recycling), obtain the thick polyimide solution of homogeneous phase transparent; Wherein, the aromatic dicarboxylic primary amine is 1 with the ratio of the mole number of aromatic series quaternary primary amine: 0.1-10; The mole number of aromatic dicarboxylic anhydride equals aromatic series quaternary primary amine, aromatic dicarboxylic primary amine and 2, the mole number sum of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-; The envelope-bulk to weight ratio of strong polar non-proton organic solvent and total reactant is 3 milliliters-10 milliliters: 1 gram, the weight of total reactant comprises aromatic dicarboxylic primary amine, aromatic series quaternary primary amine, 2, the weight sum of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, aromatic series dianhydride and single acid anhydride; An acidic catalyst is 1 with the ratio of the mole number of aromatic dicarboxylic anhydride: 1-20; Azeotropy dehydrant is 1 with the volume ratio of strong polar non-proton organic solvent: 1-10.
Described aromatic series quaternary primary amine is selected from 1, two (2, the 4-diamino phenoxy) benzene of 4-, 1, two (2, the 4-diamino phenoxy) benzene of 3-, 2, two [4-(2, the 4-diamino phenoxy) phenyl] propane of 2-, 2,2-pair [4-(2,4-diamino phenoxy phenyl] HFC-236fa, 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide, 4,4 '-two (2, the 4-diamino phenoxy) diphenyl sulfide, 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether, 4,4 '-two (2, the 4-diamino phenoxy) biphenyl, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-in the tetramethyl biphenyl one or more;
Described single acid anhydride is selected from one or more in maleic anhydride carbic anhydride, methyl carbic anhydride, the 4-phenylacetylene phthalic anhydride;
Described aromatic dicarboxylic primary amine is selected from 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 4-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (3-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (4-amino-benzene oxygen) toluene of 6-, 2, two (4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (4-amino-benzene oxygen) toluene of 5-, 2, two (4-amino-benzene oxygen) tert-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two 2.2-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-diamino-4 " hydroxyl tritane; 3; 3 '-diamino-4; 4 '-dihydroxybiphenyl; 3; 3 '-dihydroxyl-4,4 '-benzidine, 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3, one or more in the 5-diaminobenzoic acid;
Described aromatic dicarboxylic anhydride is selected from 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic biphenyl dianhydride, 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydrides of 2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 4-, 1,3-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 3,3 ', 4,4 '-in the tetracarboxylic phenyl ether dianhydride one or more;
Described strong polar non-proton organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO);
Described an acidic catalyst is selected from p-methyl benzenesulfonic acid, a toluene sulfonic acide, o-methyl-benzene sulfonic acid, adjacent acid dimethyl, in ethyl phenenyl azochlorosulfonate acid, an ethyl phenenyl azochlorosulfonate acid, the adjacent ethyl phenenyl azochlorosulfonate acid one or more;
Described entrainer is selected from one or more in benzene,toluene,xylene, ethylbenzene, diethylbenzene, monochloro-benzene, a chlorotoluene, the dichloro-toluene.
The Molecular Structure Design of polyimide carbon fiber sizing agent of the present invention is mainly based on following mechanism: (1) has good organic solvent solubility; (2) has certain chemical reactivity with the RTM polyimide resin; (3) contain strong polarity cyano group, can have the good interface performance: (4) high thermal resistance and good tack with carbon fiber.
Beneficial effect
(1) preparation method's reaction conditions gentleness of the present invention, reaction process 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 corrosives, and organic solvent uses the few and easy recovery of kind, and Recycling repeatedly is environmentally friendly;
(2) the used synthesis technique equipment of preparation process is universal, can utilize the suite of equipment of existing production polyimide resin to implement the present invention fully, is very beneficial for the industrialization of product;
(3) the material resin molecular weight of Cai Yonging is controlled easily, and molecular structure is also adjusted easily, help preparing the polyimide setting agent of ideal performance, and this setting agent has excellent size stability, mechanical property and thermotolerance.
Description of drawings
Fig. 1 is the general formula of molecular structure of polyimide carbon fiber sizing agent;
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 and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications 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
With 2 of 54.8 grams (0.1 mole), 2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] HFC-236fa and 5520 milliliters of N, the N-N,N-DIMETHYLACETAMIDE is put into reactor, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, the maleic anhydride that adds 19.6 grams (0.2 mole), in 0 ℃-20 ℃ temperature range, stir, fully after the dissolving, keep reaction 0.5 hour, add 2 of 568.5 grams (1.0 moles), two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, 518.5 2 of gram (1.0 moles), two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, 3,3 of adding 676.2 grams (2.1 moles) ', 4,4 '-tetracarboxylic acid benzophenone dianhydride, in 0 ℃-20 ℃ temperature range, stir, fully after the dissolving, keep reaction after 2 hours, add 552 milliliters of toluene and 18.8 gram (0.11 mole) p-methyl benzenesulfonic acids, heat temperature raising, the reflux water-dividing reaction is after 5 hours, tell toluene (recycling), obtain the thick polyimide solution of homogeneous phase transparent.
This polyimide solution that takes a morsel evenly is coated on the clean sheet glass, and gauge control is in the 5-10 micrometer range, and heat temperature raising obtains Kapton to remove organic solvent.Adopt fourier transform infrared spectroscopy to detect, find that this film has tangible imide ring vibration performance absorption peak (1720.45cm
-1, 1782.33cm
-1, 1385.21cm
-1) and the charateristic avsorption band (2222.15cm of cyano group
-1).
With the polyimide solution Treatment of Carbon premolding idiosome of above-mentioned gained, organic solvent (recovery) is removed in thermal radiation and vacuum devolatilization, obtains carbon fiber/polyamide imines preform.This polyimide is good to the adhesivity of carbon fiber, shape conservation rate height, and manufacturability is good.
The molecular structural formula of the polyimide setting agent in the present embodiment is as follows:
Embodiment 2
With 2 of 44.1 grams (0.1 mole), 2-is two, and [4-(2, the 4-diamino phenoxy) phenyl] propane, 1000 milliliters of N-N-methyl-2-2-pyrrolidone N-s and 5979 milliliters of N, dinethylformamide is put into reactor, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, 32.8 add the carbic anhydride of gram (0.2 mole), in 0 ℃-20 ℃ temperature range, stir, fully after the dissolving, keep reaction 2 hours, add 2 of 56.8 grams (0.1 mole), two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, 200.2 4 of gram (0.5 mole), 4 '-two (4-amino-benzene oxygen) diphenyl sulfide, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, add 2 of 364.0 grams (0.7 mole), two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-, in 0 ℃-20 ℃ temperature range, stir, after the dissolving, keep reaction after 4 hours fully, add 5979 milliliters of toluene, 1000 milliliters of dimethylbenzene and 119.7 gram (0.7 mole) p-methyl benzenesulfonic acids, heat temperature raising, the reflux water-dividing reaction was told toluene and dimethylbenzene (recycling) after 12 hours, obtained the thick polyimide solution of homogeneous phase transparent.
This polyimide solution that takes a morsel evenly is coated on the clean sheet glass, and gauge control is in the 5-10 micrometer range, and heat temperature raising obtains Kapton to remove organic solvent.Adopt fourier transform infrared spectroscopy to detect, find that this film has tangible imide ring vibration performance absorption peak (1728.11cm
-1, 1784.13cm
-1, 1386.42cm
-1) and the charateristic avsorption band (2222.46cm of cyano group
-1).
With the polyimide solution Treatment of Carbon premolding idiosome of above-mentioned gained, organic solvent (recovery) is removed in thermal radiation and vacuum devolatilization, obtains carbon fiber/polyamide imines preform.This polyimide is good to the adhesivity of carbon fiber, shape conservation rate height, and manufacturability is good.
The molecular structural formula of the polyimide setting agent in the present embodiment is as follows:
Embodiment 3
With 1 of 322.0 grams (1.0 moles), 3-two (2, the 4-diamino phenoxy) benzene and 5000 milliliters of N, the N-N,N-DIMETHYLACETAMIDE is put into reactor, stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, the maleic anhydride that adds 19.6 grams (0.2 mole), in 0 ℃-20 ℃ temperature range, stir, fully after the dissolving, keep reaction 1.5 hours, add 2 of 56.8 grams (0.1 mole), two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, 65.4 2 of gram (0.1 mole), two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-stir, fully after the dissolving, ice-water bath is cooled to 0 ℃, 3,3 of adding 372.0 grams (1.2 moles) ', 4,4 '-tetracarboxylic acid phenyl ether dianhydride, in 0 ℃-20 ℃ temperature range, stir, fully after the dissolving, keep reaction after 3 hours, add 800 milliliters of toluene and 18.8 gram (0.11 mole) p-methyl benzenesulfonic acids, heat temperature raising, the reflux water-dividing reaction is after 8 hours, tell toluene (recycling), obtain the thick polyimide solution of homogeneous phase transparent.
This polyimide solution that takes a morsel evenly is coated on the clean sheet glass, and gauge control is in the 5-10 micrometer range, and heat temperature raising obtains Kapton to remove organic solvent.Adopt fourier transform infrared spectroscopy to detect, find that this film has tangible imide ring vibration performance absorption peak (1720.98cm
-1, 1781.42cm
-1, 1382.54cm
-1) and the charateristic avsorption band (2220.47cm of cyano group
-1).
With the polyimide solution Treatment of Carbon premolding idiosome of above-mentioned gained, organic solvent (recovery) is removed in thermal radiation and vacuum devolatilization, obtains carbon fiber/polyamide imines preform.This polyimide is good to the adhesivity of carbon fiber, shape conservation rate height, and manufacturability is good.
The molecular structural formula of the polyimide setting agent in the present embodiment is as follows:
Claims (12)
1. polyimide carbon fiber sizing agent, its general formula of molecular structure is:
Wherein :-Q
1-be aromatic binary primary amine residue;=Ar=is the aromatic dicarboxylic anhydride residue;-Q
2The connection base of-aromatic series quaternary primary amine;-R-is single acid anhydride residue; M, n, p are more than or equal to 1, and less than 20 natural number, independent separately uncorrelated mutually;
Proterties: the thick solution of homogeneous phase transparent.
2. a kind of polyimide carbon fiber sizing agent according to claim 1 is characterized in that: the molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent.
3. a kind of polyimide carbon fiber sizing agent according to claim 1 is characterized in that: the molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent.
4. a kind of polyimide carbon fiber sizing agent according to claim 1 is characterized in that: the molecular structure of described polyimide carbon fiber sizing agent is:
Proterties: the thick solution of homogeneous phase transparent.
5. the preparation method of a polyimide carbon fiber sizing agent comprises:
Aromatic series quaternary primary amine and single acid anhydride were dissolved in strong polar non-proton organic solvent in 1: 2 in molar ratio, in 0 ℃-20 ℃ temperature range after stirring reaction 0.5-2 hour, add aromatic dicarboxylic primary amine and 2, two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, after the stirring and dissolving, the ice-water bath cooling, add aromatic dicarboxylic anhydride, stir, after 2-4 hour, add an acidic catalyst and entrainer in 0 ℃-20 ℃ temperature range internal reactions, reflux divides the water reaction after 5-12 hour, tell entrainer with recycling, obtain the thick polyimide solution of homogeneous phase transparent; Wherein, the aromatic dicarboxylic primary amine is 1 with the ratio of the mole number of aromatic series quaternary primary amine: 0.1-10; The mole number of aromatic dicarboxylic anhydride equals aromatic series quaternary primary amine, aromatic dicarboxylic primary amine and 2, the mole number sum of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-; The envelope-bulk to weight ratio of strong polar non-proton organic solvent and total reactant is 3 milliliters-10 milliliters: 1 gram, the weight of total reactant comprises aromatic dicarboxylic primary amine, aromatic series quaternary primary amine, 2, the weight sum of two [3-amino-4-(4-cyano-benzene oxygen) phenyl] HFC-236fa of 2-, aromatic series dianhydride and single acid anhydride; An acidic catalyst is 1 with the ratio of the mole number of aromatic dicarboxylic anhydride: 1-20; Azeotropy dehydrant is 1 with the volume ratio of strong polar non-proton organic solvent: 1-10.
6. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5, it is characterized in that: described aromatic series quaternary primary amine is selected from 1, two (2, the 4-diamino phenoxy) benzene of 4-, 1, two (2, the 4-diamino phenoxy) benzene of 3-, 2, two [4-(2, the 4-diamino phenoxy) phenyl] propane of 2-, 2,2-pair [4-(2,4-diamino phenoxy phenyl] HFC-236fa, 4,4 '-two (2, the 4-diamino phenoxy) sulfobenzide, 4,4 '-two (2, the 4-diamino phenoxy) diphenyl sulfide, 4,4 '-two (2, the 4-diamino phenoxy) phenyl ether, 4,4 '-two (2, the 4-diamino phenoxy) biphenyl, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2, the 4-diamino phenoxy)-3,3 ', 5,5 '-in the tetramethyl biphenyl one or more.
7. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5, it is characterized in that: described single acid anhydride is selected from one or more in maleic anhydride, carbic anhydride, methyl carbic anhydride, the 4-phenylacetylene phthalic anhydride;
8. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5, it is characterized in that: described aromatic dicarboxylic primary amine is selected from 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 1, two (3-amino-benzene oxygen) benzene of 4-, 2, two (4-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (3-amino-benzene oxygen) cyanobenzenes of 6-, 2, two (4-amino-benzene oxygen) toluene of 6-, 2, two (4-amino-benzene oxygen) phenylfluoroforms of 6-, 2, two (4-amino-benzene oxygen) toluene of 5-, 2, two (4-amino-benzene oxygen) tert-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) sulfobenzide, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 3-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(2-trifluoromethyl-4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) toluene of 5-, 2, two (2-trifluoromethyl-4-amino-benzene oxygen) tert.-butylbenzenes of 5-, 2,5-di-t-butyl-1, two (2-trifluoromethyl-4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) sulfobenzide, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl diphenyl sulfone, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) biphenyl, 4,4 '-two (2-trifluoromethyls-4-amino-benzene oxygen)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (2-trifluoromethyl-4-amino-benzene oxygen) phenyl ether, 4,4 '-two (4-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) phenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfide, 4,4 '-two (4-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 4,4 '-two (3-amino-benzene oxygens)-3,3 ' 5,5 '-tetramethyl biphenyl, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-diamino-4 " hydroxyl tritane; 3; 3 '-diamino-4; 4 '-dihydroxybiphenyl; 3; 3 '-dihydroxyl-4,4 '-benzidine, 2, two (the 3-amino-4-hydroxy phenyl) propane of 2-, 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, 3,3 '-diamino-4,4 '-dihydroxy diphenylsulphone, 3, one or more in the 5-diaminobenzoic acid.
9. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5, it is characterized in that: described aromatic dicarboxylic anhydride is selected from 3,3 ', 4,4 '-tetracarboxylic benzophenone dianhydride, 3,3 ', 4,4 '-the tetracarboxylic biphenyl dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydrides of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) biphenyl dianhydride, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene dianhydride, 1, two (3, the 4-di carboxyl phenyloxy) benzene dianhydrides of 3-, 3,3 ', 4,4 '-in the tetracarboxylic phenyl ether dianhydride one or more.
10. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5, it is characterized in that: described strong polar non-proton organic solvent is selected from N, in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-ethyl-2-pyrrolidone, the dimethyl sulfoxide (DMSO) one or more.
11. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5 is characterized in that: described an acidic catalyst is selected from p-methyl benzenesulfonic acid, a toluene sulfonic acide, o-methyl-benzene sulfonic acid, adjacent acid dimethyl, in ethyl phenenyl azochlorosulfonate acid, an ethyl phenenyl azochlorosulfonate acid, the adjacent ethyl phenenyl azochlorosulfonate acid one or more.
12. the preparation method of a kind of polyimide carbon fiber sizing agent according to claim 5 is characterized in that: described entrainer is selected from one or more in benzene,toluene,xylene, ethylbenzene, diethylbenzene, monochloro-benzene, a chlorotoluene, the dichloro-toluene.
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| CN106117554B (en) * | 2016-07-29 | 2019-02-26 | 东华大学 | A kind of siliceous epoxy acid imide matrix resin of BDADDS type and preparation method thereof |
| CN106633871A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | 6FDA (4,4'-hexafluoroisopropylidene)-diphthalic anhydride) type 14BDAPB branched polyimide resin film and preparation method thereof |
| CN106519675A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type bisphenol-A tetramine branched polyimide resin film and preparation method thereof |
| CN106519669A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BPDA type bisphenol A tetramine branched polyimide resin thin film and preparation method thereof |
| CN106633873A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | PMDA type bisphenol A tetramine branched polyimide resin film and a preparing method thereof |
| CN108148411B (en) * | 2018-01-15 | 2020-06-02 | 吉林大学 | Thermally processable low-Tg cyano-group-containing polyimide, polyimide film, polyimide powder and application thereof |
| CN109162101B (en) * | 2018-07-11 | 2021-03-26 | 中国航发北京航空材料研究院 | Low-viscosity high-heat-resistance polyimide fiber sizing agent and preparation method thereof |
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