CN102775789B - Thermosetting compound fluorine-containing polyimide resin and preparation method thereof - Google Patents
Thermosetting compound fluorine-containing polyimide resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermosetting compound fluorine-containing polyimide resin and a preparation method thereof, which aim at further improving the heat stability, temperature resistance and cold resistance of materials. The thermosetting compound fluorine-containing polyimide resin is prepared by compounding a component A and a compound B, wherein the mass ratio of the component A to the compound B is 1:(1-4); the component A is bisphenol AF-matrix fluorine-containing polyimide solution with the solid content of 10wt%-20wt%; and the component B is bisphenol AF phenoxy fluorine-containing polyimide solution with the solid content of 10wt%-20wt%. The thermosetting compound fluorine-containing polyimide resin has high dissolubility, heat stability, mechanical properties and melt processing performance. Besides, the preparation method is simple to operate, low in cost and environment-friendly, and can be adapted to the requirements of industrial production.
Description
Technical field
The present invention relates to polymer novel material and preparation field thereof, compound fluorinated polyimide resin of especially a kind of thermoset and preparation method thereof.
Background technology
Polyimide has excellent especially heat-resisting, low temperature resistant, fire-retardant, electrical and mechanical properties, therefore, it is as a very excellent macromolecular material of class over-all properties, be widely used in the high-tech areas such as electronics microelectronics, aerospace, space technology, laser, photoelectricity, the for example main duct of aircraft engine, by-pass air duct, high speed blade, jet valve, the empennage of cruise missile, instrument compartment section, housing etc.
Yet polyimid-base resin also exists some shortcomings, has affected to a certain extent its application in practice.The shortcoming of polyimid-base resin mainly comprises: it is insoluble to most of organic solvents, processing difficulties, and bad adhesion, water-intake rate is higher; Impelling strength by the prepared matrix material of polyimid-base resin is relatively poor, requires further improvement; In the prepared matrix material use procedure at high temperature of polyimid-base resin, easily produce fine fisssure etc.
In order to improve the performance of polyimide, the invention provides compound fluorinated polyimide resin of a kind of thermoset and preparation method thereof, this resin and preparation method thereof has no report.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, compound fluorinated polyimide resin of a kind of thermoset and preparation method thereof is provided, the compound fluorinated polyimide resin of thermoset of the present invention's preparation has good solubility, thermostability, mechanics mechanical property and good melt processability, simultaneously, this preparation method is simple to operate, cost is low, environmentally friendly, can adapt to the needs of suitability for industrialized production.
To achieve these goals, the present invention adopts following technical scheme:
The compound fluorinated polyimide resin of a kind of thermoset, by the A component with the B component is compound obtains, the mass ratio of A component and B component is 1: 1-4; The A component is bisphenol AF base fluorinated polyimide solution, solid content 10wt%-20wt%, and its general formula of molecular structure is:
The B component is bisphenol AF phenoxy group fluorinated polyimide solution, solid content 10wt%-20wt%, and general formula of molecular structure is as follows:
Wherein, in A component and B component
Tetravalence residue for the fluorinated aromatic dibasic acid anhydride is selected from
In one or more; N is greater than 100, and less than 1000 integer; M is greater than 100, and less than 1000 integer.
Be used for the preparation method of the compound fluorinated polyimide resin of above-mentioned thermoset, comprise:
(1) preparation take bisphenol AF base fluorinated polyimide solution as the A component
Under the protection of room temperature and rare gas element, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and the last the first aprotic, polar organic solvent are put into reactor, after stirring and dissolving is complete, add the first fluorinated aromatic dibasic acid anhydride, stirring reaction 12-24 hour, obtain the first thick resin solution of homogeneous phase transparent; In the first resin solution, add the first azeotropy dehydrant again, azeotropic reflux water-dividing stirring reaction was told the first azeotropy dehydrant after 8-12 hour, obtained bisphenol AF base fluorinated polyimide solution; Wherein, 2, the mol ratio of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and the first fluorinated aromatic dibasic acid anhydride is 1: 1, the quality of the last the first aprotic, polar organic solvent is 2, the 70%-90% of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-, the first fluorinated aromatic dibasic acid anhydride and the last the first aprotic, polar organic solvent three quality summation, the mass ratio of the first azeotropy dehydrant and the last the first aprotic, polar organic solvent is 1: 1; The general structure of the first fluorinated aromatic dibasic acid anhydride is as follows:
Wherein
, be selected from
In one or more;
(2) preparation take bisphenol AF phenoxy group fluorinated polyimide solution as the B component
Under the protection of room temperature and rare gas element, with 2, two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-and the last the second aprotic, polar organic solvent are put into reactor, after stirring and dissolving is complete, add the second fluorinated aromatic dibasic acid anhydride, stirring reaction 12-24 hour, obtain the second resin solution; In the second resin solution, add the second azeotropy dehydrant again, azeotropic reflux water-dividing stirring reaction was told the second azeotropy dehydrant after 8-12 hour, obtained bisphenol AF phenoxy group fluorinated polyimide solution; Wherein, 2, the mol ratio of two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-and the second fluorinated aromatic dibasic acid anhydride is 1: 1, the quality of the last the second aprotic, polar organic solvent is 2, the 65%-85% of two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-, the second fluorinated aromatic dibasic acid anhydride and the last the second aprotic, polar organic solvent three quality summation, the second mass ratio that boils dewatering agent and the last the second aprotic, polar organic solvent is 1: 1; The general structure of the second fluorinated aromatic dibasic acid anhydride is as follows:
Wherein
, be selected from
In one or more;
(3) preparation of the compound fluorinated polyimide resin of thermoset
A component, B component are mixed, add linking agent, stir, after 150-200 ℃ of stirring reaction 8-12 hour, filter by microporous teflon membran, namely get the compound fluorinated polyimide resin of thermoset; Wherein, the mass ratio of A component, B component is 1: 1-4, the quality of linking agent is the 0.3%-5% of A component, both quality sums of B component.
Described the last the first aprotic, polar organic solvent is selected from N, dinethylformamide, N, one or more in N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), described the last the second aprotic, polar organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
Described the first azeotropy dehydrant is selected from one or more in benzene,toluene,xylene, chloroform, and described the second azeotropy dehydrant is selected from one or more in benzene,toluene,xylene, chloroform.
Described linking agent selects one or more in tricyanic acid, triallyl cyanurate, cyanacrylate.
The aperture of described microporous teflon membran is 0.1-1.0 μ m.
Described rare gas element is a kind of in nitrogen, argon gas.
The preparation feedback equation of A component bisphenol AF base fluorinated polyimide is as follows:
The preparation feedback equation of B component bisphenol AF phenoxy group fluorinated polyimide is as follows:
For over-all propertieies such as the thermostability, the heatproof that further improve material are cold-resistant, the present invention is by the compound compound fluorinated polyimide resin of thermoset of preparing of component, thereby effectively enhances product performance.
The product of the present invention's preparation is compound by component, greatly reduces the specific inductivity of material, and specific inductivity is between 1.2～2.2.Hydroxyl in component of the present invention can improve molecular flexibility, improves solvability and the processing characteristics of product, and prepared product solubility is good, and processing characteristics and mechanical property obviously improve.Simultaneously, the present invention improves its snappiness by adding linking agent can obviously improve the polymerization degree and the moulding property of product, and the existing polyimide material of elongation at break increases doubly left and right of 5-10.The resin moulded performance of the compound fluorinated polyimide of thermoset of the present invention's preparation is good, its after heat treatment mold pressing can be prepared the resin mold casting die, also can prepare matrix material with matrix after dissolving, it can significantly improve the intensity of composite-material abrasive layer as a kind of macromolecule reinforcing material of mechanical property excellence.
The present invention adopts two kinds of products that component is compound, prepared, and it allows the life-time service temperature is 480 ℃, and permission moment use temperature can reach 600 ℃, has simultaneously resistance to low temperature preferably, even goods are become fragile.The prepared product heat-resistant stability of the present invention is good, is suitable for making high-end high temperature resistant and low temperature radiation hardness matrix material.
Fluoro-containing group in component of the present invention can reduce the water-intake rate of material, improves thermo-oxidative stability, thermosetting processibility, thermotolerance, ageing resistance and mechanical property.Benzene oxygen key in component makes product have better flame retardant resistance and self-extinguishing, is suitable for this product impregnation of carbon fibers, glass fibre and aramid fiber etc., thereby prepares high-quality prepreg, and prepared prepreg has good composite material forming processing characteristics.
In sum, the product of the present invention's preparation has solvability, thermostability, thermosetting processibility, thermotolerance, ageing resistance, mouldability and mechanical property preferably, can significantly improve molecular flexibility, greatly reduce the specific inductivity of material, be a kind of macromolecular material of excellent performance.Preparation method's technique of the present invention is simple simultaneously, is suitable for large-scale industrialization production.
Description of drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the general formula of molecular structure of bisphenol AF base fluorinated polyimide.
Fig. 2 is the general formula of molecular structure of bisphenol AF phenoxy group fluorinated polyimide.
Fig. 3 is the infrared spectrogram of the bisphenol AF base fluorinated polyimide of example 1 preparation.
Fig. 4 is the infrared spectrogram of the bisphenol AF phenoxy group fluorinated polyimide of example 1 preparation.
Fig. 5 is the infrared spectrogram of the bisphenol AF base fluorinated polyimide of example 2 preparations.
Fig. 6 is the infrared spectrogram of the bisphenol AF phenoxy group fluorinated polyimide of example 2 preparations.
Embodiment
Disclosed all features in this specification sheets, or the step in disclosed all methods or process except mutually exclusive feature and/or step, all can make up by any way.
Disclosed arbitrary feature in this specification sheets is unless special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, unless special narration, each feature is an example in a series of equivalences or similar characteristics.
At room temperature; adopt nitrogen protection; with 36.6 g (0.1mol) 2; two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and 460.0 g N-Methyl pyrrolidone are put into reactor; after stirring and dissolving is complete, add 44.4 g (0.1mol) 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids; stirring reaction 12-24 hour, obtain the first thick resin solution of homogeneous phase transparent.In the first resin solution, add 460.0 g dimethylbenzene again, after azeotropic reflux water-dividing stirring reaction 8-12h, water generation reaction and dimethylbenzene azeotropic steam, and obtain bisphenol AF base fluorinated polyimide solution, and solid content is 13wt%, i.e. A component, and yield is 95%.
At room temperature; adopt nitrogen protection; with 51.8 g (0.1mol) 2; two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-and 450.0 g N-Methyl pyrrolidone are put into reactor; after stirring and dissolving is complete, add 44.4 g (0.1mol) 4,4'-(hexafluoro isopropyl alkene) two anhydride phthalic acids; stirring reaction 12-24h under room temperature obtains the second thick resin solution of homogeneous phase transparent.In the first resin solution, add 450.0 g dimethylbenzene again, after azeotropic reflux water-dividing stirring reaction 8-12h, water generation reaction and dimethylbenzene azeotropic steam, and obtain bisphenol AF phenoxy group fluorinated polyimide solution, and solid content is 16wt%, i.e. B component, and yield is 94%.
Get 1.0 g A components and be coated on equably on clean flat glass film, put into convection oven, be warming up to 80 ℃, insulation 0.5h continues to be warming up to 150 ℃, insulation 0.5h, continue to be warming up to 250 ℃, insulation 0.5h continues to be warming up to 300 ℃, insulation 0.5h closes heating system, naturally cools to room temperature, demoulding, obtain bisphenol AF base fluorinated polyimide film, its infrared spectrogram has obvious imide charateristic avsorption band as shown in Figure 3.
Get 1.0 gram B components and be coated on equably on clean flat glass film, put into convection oven, be warming up to 80 ℃, insulation 0.5h continues to be warming up to 150 ℃, insulation 0.5h, continue to be warming up to 250 ℃, insulation 0.5h continues to be warming up to 300 ℃, insulation 0.5h closes heating system, naturally cools to room temperature, demoulding, obtain bisphenol AF phenoxy group fluorinated polyimide film, its infrared spectrogram has obvious imide charateristic avsorption band as shown in Figure 4.
Get beaker, add 10.0 g A component solutions and 10.0 g B component solutions in beaker, add again linking agent triallyl cyanurate 0.15g, stir, after 195 ℃ of stirring reaction 8h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.5 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-1; Separately get beaker, add 10.0 g A component solutions and 20.0 g B component solutions in beaker, add again linking agent triallyl cyanurate 0.15g, stir, after 195 ℃ of stirring reaction 8h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.5 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-2; Separately get beaker, add 10.0 g A component solutions and 30.0 g B component solutions in beaker, add again linking agent triallyl cyanurate 0.15g, stir, after 195 ℃ of stirring reaction 8h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.5 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-3.
PIF-1 obtained above, PIF-2, PIF-3 resin matrix solution are carried out compound preparation preimpregnation cloth with carbon cloth on wrapping machine, after most of solvent that volatilizees, the laying that superposes, the prepreg after laying is made preimpregnation cloth after 50-220 ℃ of temperature programming (per hour heating up 30 ℃) processed.Preimpregnation cloth is put into and is preheating to the press of 260 ℃, at 350 ℃ of pressure that apply 1MPa, then is cured crosslinkedly at 400 ℃ of heat-insulation pressure keeping 2h, and when naturally cooling to below 200 ℃, die sinking obtains the veneer sheet of composite polyimide material.The second-order transition temperature of veneer sheet is followed successively by: 435 ℃, 446 ℃, 431 ℃ (are adopted the test of DMA method, be the test of dynamic mechanical analysis method), 5% weightless temperature is followed successively by: 532 ℃, 539 ℃, 535 ℃ (adopting the test of TGA method, i.e. gravitational thermal analysis method test).
With PIF-1 obtained above, PIF-2, PIF-3 resin matrix solution, under 90-120 ℃, revolve to steam and obtain thick liquid after removing most of solvent, the thick liquid that obtains at 50-220 ℃ of lower heating, drying, is obtained the resin mold molding powder.10g resin mold molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat, be warmed up to the pressure of 350 ℃ of after-applied 1MPa, then continue to be heated to 450 ℃ of pressurizes 2 hours, remove pressure when naturally cooling to below 200 ℃, obtain the virgin resin molding.The resin glass transition temperature is followed successively by: 429 ℃, 442 ℃, 438 ℃ (adopting the test of DMA method), 5% weightless temperature is followed successively by: 528 ℃, 541 ℃, 533 ℃ (adopting the test of TGA method).
At room temperature, adopt nitrogen protection, with 36.6 g (0.1mol) 2; two (3-amino-4-hydroxylphenyl) HFC-236fa and the 460.0gN of 2-; the N-N,N-DIMETHYLACETAMIDE is put into reactor, after stirring and dissolving is complete, adds 35.4 g (0.1mol) 1; two (trifluoromethyl)-2 of 4-; 3,5,6-benzene tertacarbonic acid dianhydride; stirring reaction 12-24 hour, obtain the first thick resin solution of homogeneous phase transparent.In the first resin solution, add 460.0 g toluene again, after azeotropic reflux water-dividing stirring reaction 8-12h, water generation reaction and methylbenzene azeotropic steam, and obtain bisphenol AF base fluorinated polyimide solution, and solid content is 12wt%, i.e. A component, and yield is 93%.
At room temperature, adopt nitrogen protection, with 51.8 g (0.1mol) 2; two [4-(4-amino-benzene oxygen) benzene] HFC-236fa and the 450.0 g N of 2-; the N-N,N-DIMETHYLACETAMIDE is put into reactor, after stirring and dissolving is complete, adds 35.4 g (0.1mol) 1; two (trifluoromethyl)-2 of 4-; 3,5,6-benzene tertacarbonic acid dianhydride; stirring reaction 12-24h under room temperature obtains the second thick resin solution of homogeneous phase transparent.In the first resin solution, add 450.0 g toluene again, after azeotropic reflux water-dividing stirring reaction 8-12h, water generation reaction and methylbenzene azeotropic steam, and obtain bisphenol AF phenoxy group fluorinated polyimide solution, and solid content is 15wt%, i.e. B component, and yield is 94%.
Get 1.0 g A components and be coated on equably on clean flat glass film, put into convection oven, be warming up to 80 ℃, insulation 0.5h continues to be warming up to 150 ℃, insulation 0.5h, continue to be warming up to 250 ℃, insulation 0.5h continues to be warming up to 300 ℃, insulation 0.5h closes heating system, naturally cools to room temperature, demoulding, obtain bisphenol AF base fluorinated polyimide film, its infrared spectrogram has obvious imide charateristic avsorption band as shown in Figure 5.
Get 1.0 gram B components and be coated on equably on clean flat glass film, put into convection oven, be warming up to 80 ℃, insulation 0.5h continues to be warming up to 150 ℃, insulation 0.5h, continue to be warming up to 250 ℃, insulation 0.5h continues to be warming up to 300 ℃, insulation 0.5h closes heating system, naturally cools to room temperature, demoulding, obtain bisphenol AF phenoxy group fluorinated polyimide film, its infrared spectrogram has obvious imide charateristic avsorption band as shown in Figure 6.
Get beaker, add 10.0 g A component solutions and 10.0 g B component solutions in beaker, add again cyanacrylate 1.0g, stir, after 165 ℃ of stirring reaction 11h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.4 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-4; Separately get beaker, add 10.0 g A component solutions and 20.0 g B component solutions in beaker, add again cyanacrylate 1.0g, stir, after 165 ℃ of stirring reaction 11h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.4 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-5; Separately get beaker, add 10.0 g A component solutions and 30.0 g B component solutions in beaker, add again cyanacrylate 1.0g, stir, after 165 ℃ of stirring reaction 11h, to filter by microporous teflon membran, the aperture of this microporous teflon membran is 0.4 μ m, be cooled to room temperature and obtain product solution, be denoted as PIF-6.
PIF-4 obtained above, PIF-5, PIF-6 resin matrix solution are carried out compound preparation preimpregnation cloth with carbon cloth on wrapping machine, after most of solvent that volatilizees, the laying that superposes, the prepreg after laying is made preimpregnation cloth after 50-220 ℃ of temperature programming (per hour heating up 30 ℃) processed.Preimpregnation cloth is put into and is preheating to the press of 260 ℃, at 350 ℃ of pressure that apply 1MPa, then is cured crosslinkedly at 400 ℃ of heat-insulation pressure keeping 2h, and when naturally cooling to below 200 ℃, die sinking obtains the veneer sheet of composite polyimide material.The second-order transition temperature of veneer sheet is followed successively by: 433 ℃, 439 ℃, 434 ℃ (adopting the test of DMA method), 5% weightless temperature is followed successively by: 531 ℃, 541 ℃, 533 ℃ (adopting the test of TGA method).
PIF-4 obtained above, PIF-5, PIF-6 resin matrix solution after most of solvent is removed in 90-120 ℃ of backspin steaming, are obtained thick liquid.The thick liquid that obtains at 50-220 ℃ of lower heating, drying, is obtained the resin mold molding powder.10g resin mold molding powder is put into mould, put in the press that is preheating to 250 ℃ and heat, be warmed up to the pressure of 350 ℃ of after-applied 1MPa, then continue to be heated to 450 ℃ of pressurizes 2 hours, remove pressure when naturally cooling to below 200 ℃, obtain the virgin resin molding.The resin glass transition temperature is followed successively by: 423 ℃, 435 ℃, 426 ℃ (adopting the test of DMA method), 5% weightless temperature is followed successively by: 521 ℃, 535 ℃, 526 ℃ (adopting the test of TGA method).
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
Claims (6)
1. compound fluorinated polyimide resin of thermoset, by the A component with the B component is compound obtains, the mass ratio of A component and B component is 1: 1-4; The A component is bisphenol AF base fluorinated polyimide solution, solid content 10wt%-20wt%, and its general formula of molecular structure is:
The B component is bisphenol AF phenoxy group fluorinated polyimide solution, solid content 10wt%-20wt%, and general formula of molecular structure is as follows:
Wherein, in A component and B component
Tetravalence residue for the fluorinated aromatic dibasic acid anhydride is selected from
In one or more; N is greater than 100, and less than 1000 integer; M is greater than 100, and less than 1000 integer;
By the A component with the B component is compound obtains, the linking agent that Combined Mining is used is one or more in tricyanic acid, triallyl cyanurate, cyanacrylate.
2. be used for the preparation method of the compound fluorinated polyimide resin of above-mentioned thermoset, comprise:
(1) preparation take bisphenol AF base fluorinated polyimide solution as the A component
Under the protection of room temperature and rare gas element, with 2, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and the last the first aprotic, polar organic solvent are put into reactor, after stirring and dissolving is complete, add the first fluorinated aromatic dibasic acid anhydride, stirring reaction 12-24 hour, obtain the first thick resin solution of homogeneous phase transparent; In the first resin solution, add the first azeotropy dehydrant again, azeotropic reflux water-dividing stirring reaction was told the first azeotropy dehydrant after 8-12 hour, obtained bisphenol AF base fluorinated polyimide solution; Wherein, 2, the mol ratio of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-and the first fluorinated aromatic dibasic acid anhydride is 1:1, the quality of the last the first aprotic, polar organic solvent is 2, the 70%-90% of two (3-amino-4-hydroxylphenyl) HFC-236fa of 2-, the first fluorinated aromatic dibasic acid anhydride and the last the first aprotic, polar organic solvent three quality summation, the mass ratio of the first azeotropy dehydrant and the last the first aprotic, polar organic solvent is 1: 1; The general structure of the first fluorinated aromatic dibasic acid anhydride is as follows:
Wherein
, be selected from
In one or more;
(2) preparation take bisphenol AF phenoxy group fluorinated polyimide solution as the B component
Under the protection of room temperature and rare gas element, with 2, two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-and the last the second aprotic, polar organic solvent are put into reactor, after stirring and dissolving is complete, add the second fluorinated aromatic dibasic acid anhydride, stirring reaction 12-24 hour, obtain the second resin solution; In the second resin solution, add the second azeotropy dehydrant again, azeotropic reflux water-dividing stirring reaction was told the second azeotropy dehydrant after 8-12 hour, obtained bisphenol AF phenoxy group fluorinated polyimide solution; Wherein, 2, the mol ratio of two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-and the second fluorinated aromatic dibasic acid anhydride is 1: 1, the quality of the last the second aprotic, polar organic solvent is 2, the 65%-85% of two [4-(4-amino-benzene oxygen) benzene] HFC-236fa of 2-, the second fluorinated aromatic dibasic acid anhydride and the last the second aprotic, polar organic solvent three quality summation, the second mass ratio that boils dewatering agent and the last the second aprotic, polar organic solvent is 1: 1; The general structure of the second fluorinated aromatic dibasic acid anhydride is as follows:
Wherein
, be selected from
In one or more;
(3) preparation of the compound fluorinated polyimide resin of thermoset
A component, B component are mixed, add linking agent, stir, after 150-200 ℃ of stirring reaction 8-12 hour, filter by microporous teflon membran, namely get the compound fluorinated polyimide resin of thermoset; Wherein, the mass ratio of A component, B component is 1: 1-4, and the quality of linking agent is the 0.3%-5% of A component, both quality sums of B component;
Described linking agent is one or more in tricyanic acid, triallyl cyanurate, cyanacrylate.
3. the preparation method of the compound fluorinated polyimide resin of thermoset according to claim 2, it is characterized in that, described first, second strong aprotic, polar organic solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO).
4. the preparation method of the compound fluorinated polyimide resin of thermoset according to claim 2, is characterized in that, described first, second azeotropy dehydrant is selected from one or more in benzene,toluene,xylene, chloroform.
5. the preparation method of the compound fluorinated polyimide resin of thermoset according to claim 2, is characterized in that, the aperture of described microporous teflon membran is 0.1-1.0 μ m.
6. the preparation method of according to claim 2-5 compound fluorinated polyimide resins of arbitrary described thermoset, is characterized in that, described rare gas element is a kind of in nitrogen, argon gas.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1184403A2 (en) * | 2000-06-29 | 2002-03-06 | Shin-Etsu Chemical Co., Ltd. | Polyimide silicone resin, process for its production, and polyimide silicone resin composition |
| CN101289543A (en) * | 2008-06-06 | 2008-10-22 | 东华大学 | Method for preparing 1,4-di(2,4-diamino phenoxy)benzenoid form polyimide film for flexible copper clad plate |
| CN101560298A (en) * | 2009-05-26 | 2009-10-21 | 东华大学 | Thermoplastic fluorine-containing fully aromatic polyimide powder and preparation method thereof |
| CN101921482A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Thermosetting polyimide resin and preparation method thereof |
-
2012
- 2012-08-15 CN CN 201210288861 patent/CN102775789B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1184403A2 (en) * | 2000-06-29 | 2002-03-06 | Shin-Etsu Chemical Co., Ltd. | Polyimide silicone resin, process for its production, and polyimide silicone resin composition |
| CN101289543A (en) * | 2008-06-06 | 2008-10-22 | 东华大学 | Method for preparing 1,4-di(2,4-diamino phenoxy)benzenoid form polyimide film for flexible copper clad plate |
| CN101560298A (en) * | 2009-05-26 | 2009-10-21 | 东华大学 | Thermoplastic fluorine-containing fully aromatic polyimide powder and preparation method thereof |
| CN101921482A (en) * | 2010-08-18 | 2010-12-22 | 东华大学 | Thermosetting polyimide resin and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 6FDA型聚酰亚胺的合成及其分子量调控;伍慧雯等;《功能高分子学报》;20120630;第25卷(第2期);第152-158页 * |
| 伍慧雯等.6FDA型聚酰亚胺的合成及其分子量调控.《功能高分子学报》.2012,第25卷(第2期), |
| 基于双酚AF的含氟聚酰亚胺单体合成;施险峰等;《化工新型材料》;20120430;第40卷(第4期);第62-71页 * |
| 施险峰等.基于双酚AF的含氟聚酰亚胺单体合成.《化工新型材料》.2012,第40卷(第4期), |
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