CN101654518B - Thermosetting polyimide resin and preparation method and application thereof - Google Patents
Thermosetting polyimide resin and preparation method and application thereof Download PDFInfo
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- CN101654518B CN101654518B CN2009100939220A CN200910093922A CN101654518B CN 101654518 B CN101654518 B CN 101654518B CN 2009100939220 A CN2009100939220 A CN 2009100939220A CN 200910093922 A CN200910093922 A CN 200910093922A CN 101654518 B CN101654518 B CN 101654518B
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Abstract
The invention discloses norbornene-blocked polyimide resin, a preparation method and the application thereof. The structural formula of the polyimide resin is shown in formula I. The polyimide resin of the invention is prepared from the raw materials of reactive blocking agent, aromatic tetracid dihydride and aromatic diamine by a PMR method. The polyimide resin of the invention can also be processed by heat treatment to obtain resin moulding powder having low melt viscosity, and a pure resin moulding piece with high mechanical property and favorable heat-resistant property can be obtained after thermofixation. The polyimide resin is suitable for steeping carbon fiber, fiber glass or aramid fiber and the like to be prepared into prepreg; and the prepreg has favorable contour machining property, and a composite material with low poriness, high mechanical property and favorable heat-resistant peroperty can be obtained after 50 to 320 DEG C thermofixation molding by a hot mould pressing or a vacuum autoclave technology. The composite material can be used for preparing heat resisting components in the fields of aviation, space flight, space technology, and the like, and can be used for a long time under the temperature from 350 to 370 DEG C.
Description
Technical field
The present invention relates to a kind of thermoset polyimide resin and preparation method thereof and application.
Background technology
Thermoset polyimide resin has the heat-resisting oxidative stability and the mechanical property of high second-order transition temperature, excellence, with it is that the matrix material of resin matrix and the compound preparation of carbon fiber is the highest polymer matrix composites of present temperature resistant grade, has important use in fields such as Aeronautics and Astronautics, space technologies as light weight, resistant to elevated temperatures structural part and is worth.Kind according to the reactive end-capping reagent that is adopted, thermoset polyimide resin mainly is divided into three major types such as bimaleimide resin, PMR polyimide type resin and the end capped polyimide resin of benzyne base, wherein the most representative PMR polyimide type resin is that (U.S.Patent 3 for the PMR-15 resin, 745,149), its temperature classification is 316 ℃, by the matrix material of itself and the compound preparation of carbon fiber can be under 316 ℃ high temperature life-time service.PMR-II-50 (NASA-TM-X-71894) has higher resistance toheat, and its temperature classification is 371 ℃.But this resin is because melting behaviour is poor, and building-up properties is low, is difficult to prepare the composite element of large-scale or complicated shape.
In recent years, it is found that the thermoset polyimide resin that contains asymmetric dibenzoyl imine structure has good melting behaviour and comprises low melt viscosity and melt temperature and good melt stability, its thermofixation thing has higher heat resistance simultaneously.It is end-capping reagent that United States Patent (USP) (U.S.Patent 5,432,001, U.S.Patent 5,461,138, U.S.Patent5,461,137) discloses the norbornylene dicarboxylic acid anhydride, contains the polyimide resin of asymmetric dibenzoyl imine structure.But the melt viscosity height behind these resin heating and meltings can only be suitable for hot compression molding technology and prepare carbon fibre reinforced composite under 320 ℃ of high temperature.(U.S.Patent 7 for United States Patent (USP), 015, it is end capped 304B1) to disclose a kind of phenylacetylene base, the polyimide resin that contains asymmetric dibenzoyl imine structure, this resin has very low melt viscosity, can be suitable for resin transfer molding technology, be used to prepare anti-288-343 ℃ carbon fibre reinforced composite.But this resin need (＞370 ℃) just can be finished the thermofixation crosslinking reaction under higher temperature.
Therefore, it is significant for development high-temperature resistance carbon fiber reinforced composite that development has the polyimide resin of good melting behaviour, low solidification value, high heat resistance energy and strong mechanical performance.
Summary of the invention
The purpose of this invention is to provide a kind of thermoset polyimide resin and preparation method thereof.
Provided by the present invention is a kind of thermoset polyimide resin with low melt viscosity, high heat resistance energy, this polyimide resin not only is suitable for hot compression molding technology, but also being suitable for autoclave forming process, the fibre reinforced composites that prepare at 320 ℃ of high temperature compacted unders have good resistance toheat and comprehensive mechanical property.
The general structure of polyimide resin provided by the present invention is suc as formula shown in the I,
(formula I)
Among the formula I,
Or
Described m=1-20, n=0.01-6.
The number-average molecular weight that calculates described polyimide resin according to the ratio of used end-capping reagent, aromatic series tetracarboxylic dianhydride and aromatic diamine is 1000-9000 (because polyimide is poorly soluble, can't use the determination of experimental method molecular weight).
The preparation method of above-mentioned polyimide resin may further comprise the steps:
1) end-capping reagent and organic fatty alcoholic solvent are carried out esterification, obtain end-capping reagent list acid monoester solution;
2) aromatic series tetracarboxylic dianhydride and organic fatty alcoholic solvent are carried out esterification, obtain aromatic series tetracid two ester solutions;
3) aromatic diamine is dissolved in the organic fatty alcoholic solvent, adds end-capping reagent list acid monoester solution, the step 2 of step 1) then successively) aromatic series tetracid two ester solutions react, obtain the polyimide resin solution shown in the formula I;
Wherein, described end-capping reagent is the compound shown in the formula II,
(formula II);
Described aromatic series tetracarboxylic dianhydride is the mixture of following aromatic series tetracarboxylic dianhydride I and aromatic series tetracarboxylic dianhydride II, and wherein, the ratio of quality and the number of copies of aromatic series tetracarboxylic dianhydride I and aromatic series tetracarboxylic dianhydride II is 100: 1-30;
Described aromatic series tetracarboxylic dianhydride I is selected from shown in following formula A1, formula A2, the formula A3 a kind of in the compound:
Formula A1 formula A2 formula A3
Described aromatic series tetracarboxylic dianhydride II is selected from shown in following formula B1, formula B2, the formula B3 a kind of in the compound:
Formula B1 formula B2 formula B3
Described aromatic diamine is selected from a kind of in the following compound:
Ursol D mphenylenediamine 4,4 '-benzidine 4,4 '-diaminodiphenyl oxide
3,4 '-diaminodiphenyl oxide 4,4 '-diaminodiphenylmethane 4,4 '-diaminobenzophenone
4,4 '-diaminodiphenylsulfone(DDS) 2,2 '-dimethyl-4,4 '-benzidine 2,2 '-two trifluoromethyls-4,4 '-benzidine
2,2 ', 6,6 '-tetramethyl--4,4 '-benzidine 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-
2,2-two (4-(4-aminophenyl) HFC-236fa 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-
1, two (the 4-amino-benzene oxygens) 1 of 4-, two (4-amino-benzene oxygen) benzene of 3-
1, two (3-amino-benzene oxygen) benzene 1 of 3-, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 4-
4,4 '-two (4-amino-benzene oxygen) biphenyl 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl
The ratio of quality and the number of copies of described end-capping reagent, aromatic series tetracarboxylic dianhydride and aromatic diamine is followed successively by 5-80: 100: 30-150.
The temperature of reaction of reacting described in the step 3) is 5-40 ℃, and the reaction times is 1-10 hour.
Wherein, step 1), step 2) and step 3) described in the organic fatty alcoholic solvent be at least a methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, the trimethyl carbinol in the following alcohol; Or be the arbitrary proportion blended mixture of a kind of and following at least a solvent in the above-mentioned alcohol: acetone, tetrahydrofuran (THF), dioxane, benzene, toluene, chloroform and methylene dichloride.
The ratio of quality and the number of copies of end-capping reagent described in the step 1) and organic fatty alcoholic solvent can be 5-80: 5-600; 1) esterification described in is carried out under the condition of 65-140 ℃ of reflux, and the reaction times can be 1-6 hour.
The ratio of quality and the number of copies of tetracarboxylic dianhydride of aromatic series step 2) and organic fatty alcoholic solvent can be 100: 60-1200; Step 2) esterification described in is carried out under the condition of 65-140 ℃ of reflux, and the reaction times can be 1-6 hour.
The mass fraction of aromatic diamine described in the step 3) and organic fatty alcoholic solvent is comparable to be 30-150: 10-800.
The solution of polyimide resin provided by the present invention also can after heat treatment obtain resin mold molding powder (being solid-state polyimide resin), the molding powder has low melt viscosity, obtains the virgin resin molding of mechanical property height, fine heat-resisting performance after thermofixation.
A further object of the present invention provides the application of the polyimide resin shown in the formula I in preparation polyimide resin based composites.Polyimide resin of the present invention is suitable for impregnation of carbon fibers, glass fibre or aramid fiber etc., makes prepreg (band or cloth); This prepreg has good moulding processability, adopts hot moulding or vacuum hotpressing jar technology can obtain after 50-320 ℃ thermofixation moulding that porosity is low, mechanical property is high, the matrix material of fine heat-resisting performance.The second-order transition temperature of described matrix material can be used for preparing the high temperature resistant component in fields such as Aeronautics and Astronautics, space technology, life-time service under 350-370 ℃ of environment between 350-450 ℃.
Embodiment
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
The structural formula of the A1 among the following embodiment, A2, A3, B1, B2, B3 compound is as follows:
The performance of the preparation of embodiment 1, polyimide resin and resin mold casting die
1) 36 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 86 ℃ of reflux in 48 mass parts ethanol was obtained norbornylene diformate mono ester solution (NE) in 4 hours.
2) with 90 mass parts compd As
183 ℃ of reflux obtained compd A in 3 hours in 135 mass parts ethanol
1Carboxylate solution, with 10 mass parts compd Bs
185 ℃ of reflux obtained compd B in 4 hours in 15 mass parts ethanol
1Carboxylate solution.
3) 50 mass parts mphenylenediamines are dissolved in the 68 mass parts ethanol, stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
1Carboxylate solution, 20 ℃ of following stirring reactions 8 hours, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1530, m is 2.79 among the formula I, n is 0.28.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 70 ℃/3h, 140 ℃/2h, 200 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 70Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 380 ℃ (adopting the DMA method to measure), and tensile strength is greater than 85MPa, and flexural strength is greater than 130MPa.
The performance of the preparation of embodiment 2, polyimide resin and carbon fiber composite polyimide material veneer sheet
1) 28 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 68 ℃ of reflux in 31 mass parts methyl alcohol was obtained corresponding norbornylene diformate mono ester solution (NE) in 2 hours.
2) with 72 mass parts compd As
169 ℃ of reflux obtained compd A in 3 hours in 80 mass parts methyl alcohol
1Carboxylate solution, with 9 parts of compd Bs
270 ℃ of reflux obtained compd B in 5 hours in 9 mass parts methyl alcohol
2Carboxylate solution.
3) with 72 mass parts 3,4 '-diaminodiphenyl oxide is dissolved in the 60 mass parts methyl alcohol, and stirring adds NE, compd A after half an hour successively
1And B
2Carboxylate solution, stirred 5 hours down at 30 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1970, m is 2.87 among the formula I, n is 0.34.
The resin solution that step 3) is obtained carries out compound preparation prepreg with carbon fiber on wrapping machine, prepreg is carried out cutting, shop layer, obtains carbon fiber composite polyimide material veneer sheet after the thermofixation under 50-320 ℃ and 3MPa pressure.
The second-order transition temperature that records this veneer sheet is greater than 360 ℃ (adopting the DMA method to measure), and flexural strength is greater than 1400MPa, and modulus in flexure is greater than 100GPa, and interlaminar shear strength is greater than 80MPa.
The performance of the preparation of embodiment 3, polyimide resin and resin mold casting die
1) 19 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 70 ℃ of reflux in 22 mass parts methyl alcohol was obtained norbornylene diformate mono ester solution (NE) in 2 hours.
2) with 37 mass parts compd As
284 ℃ of reflux obtained compd A in 5 hours in 52 mass parts ethanol
2Carboxylate solution, with 9 mass parts compd Bs
185 ℃ of reflux obtained compd B in 2 hours in 13 mass parts ethanol
1Carboxylate solution.
3) with 45 mass parts 4,4 '-diaminodiphenylmethane is dissolved in the 34 mass parts methyl alcohol, and stirring adds above-mentioned NE, compd A after half an hour successively
2And B
1Carboxylate solution, stirred 4 hours down at 20 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1680, m is 1.96 among the formula I, n is 0.48.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 80 ℃/3h, 150 ℃/2h, 210 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 120Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 3MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 360 ℃ (adopting the DMA method to measure), and tensile strength is greater than 75MPa, and flexural strength is greater than 130MPa.
The performance of the preparation of embodiment 4, polyimide resin and resin mold casting die
1) 47 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 86 ℃ of reflux in 60 mass parts ethanol was obtained corresponding norbornylene diformate mono ester solution (NE) in 5 hours.
2) with 120 mass parts compd As
282 ℃ of reflux obtained compd A in 6 hours in 175 mass parts ethanol
2Carboxylate solution, with 24 mass parts compd Bs
283 ℃ of reflux obtained compd B in 4 hours in 30 mass parts ethanol
2Carboxylate solution.
3) with 175 mass parts 1, two (4-amino-benzene oxygen) benzene of 3-are dissolved in the 120 mass parts ethanol, and stirring adds NE, compd A after half an hour successively
2And B
2Carboxylate solution, stirred 4 hours down at 40 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 2390, m is 2.57 among the formula I, n is 0.54.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 80 ℃/3h, 140 ℃/2h, 220 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 8Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 350 ℃ (adopting the DMA method to measure), and tensile strength is greater than 70MPa, and flexural strength is greater than 110MPa.
The performance of the preparation of embodiment 5, polyimide resin and resin mold casting die
1) 15 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 82 ℃ of reflux in 20 mass parts ethanol was obtained norbornylene diformate mono ester solution (NE) in 2 hours.
2) with 48 mass parts compd As
368 ℃ of reflux obtained compd A in 4 hours in 46 mass parts methyl alcohol
3Carboxylate solution, with 5 mass parts compd Bs
269 ℃ of reflux obtained compd B in 4 hours in 5 mass parts methyl alcohol
2Carboxylate solution.
3) with 78 mass parts 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 4-are dissolved in the 80 mass parts ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
3And B
2Carboxylate solution, stirred 9 hours down at 25 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 3170, m is 2.93 among the formula I, n is 0.35.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 70 ℃/3h, 140 ℃/2h, 230 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 28Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 1.5MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 350 ℃ (adopting the DMA method to measure), and tensile strength is greater than 80MPa, and flexural strength is greater than 120MPa.
The performance of the preparation of embodiment 6, polyimide resin and resin mold casting die
1) 59 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 67 ℃ of reflux in 62 mass parts methyl alcohol was obtained corresponding norbornylene diformate mono ester solution (NE) in 2 hours.
2) with 193 mass parts compd As
268 ℃ of reflux obtained compd A in 5 hours in 172 mass parts methyl alcohol
2Carboxylate solution, with 20 parts of compd Bs
370 ℃ of reflux obtained compd B in 2 hours in 18 parts of methyl alcohol
3Carboxylate solution.
3) 318 mass parts 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl is dissolved in 285 parts of methyl alcohol, stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
2And B
3Carboxylate solution, stirred 5 hours down at 35 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 3640, m is 3.29 among the formula I, n is 0.25.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 60 ℃/3h, 150 ℃/2h, 230 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 45Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 360 ℃ (adopting the DMA method to measure), and tensile strength is greater than 75MPa, and flexural strength is greater than 130MPa.
The performance of the preparation of embodiment 7, polyimide resin and carbon fiber composite polyimide material veneer sheet
1) 66 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 80 ℃ of reflux in 88 mass parts ethanol was obtained norbornylene diformate mono ester solution (NE) in 6 hours.
2) with 160 mass parts compd As
181 ℃ of reflux obtained compd A in 4 hours in 225 mass parts ethanol
1Carboxylate solution, with 18 mass parts compd Bs
383 ℃ of reflux obtained compd B in 5 hours in 24 mass parts ethanol
3Carboxylate solution.
3) 54 mass parts mphenylenediamines, 36 parts of Ursol D are dissolved in the 140 mass parts ethanol, stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
3Carboxylate solution, stirred 8 hours down at 40 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1500, m is 2.71 among the formula I, n is 0.20.
The resin solution that step 3) is obtained carries out compound preparation prepreg with carbon fiber on wrapping machine, prepreg is carried out cutting, shop layer, obtains carbon fiber composite polyimide material veneer sheet after the thermofixation under 50-320 ℃ and 4MPa pressure.
The second-order transition temperature that records this veneer sheet is greater than 410 ℃ (adopting the DMA method to measure), and flexural strength is greater than 1500MPa, and modulus in flexure is greater than 130GPa, and interlaminar shear strength is greater than 60MPa.
The performance of the preparation of embodiment 8, polyimide resin and carbon fiber composite polyimide material veneer sheet
1) 26 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 84 ℃ of reflux in 33 mass parts ethanol was obtained corresponding norbornylene diformate mono ester solution (NE) in 2 hours.
2) with 54 mass parts compd As
183 ℃ of reflux obtained compd A in 6 hours in 82 mass parts ethanol
1Carboxylate solution, with 15 mass parts compd Bs
182 ℃ of reflux obtained compd B in 4 hours in 21 mass parts ethanol
1Carboxylate solution.
3) with 17 mass parts Ursol D, 31 mass parts 4,4 '-diaminodiphenyl oxide is dissolved in the 52 mass parts ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
1Carboxylate solution, stirred 7 hours down at 30 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1660, m is 2.32 among the formula I, n is 0.59.
The resin solution that step 3) is obtained carries out compound preparation prepreg with carbon fiber on wrapping machine, prepreg is carried out cutting, shop layer, obtains carbon fiber composite polyimide material veneer sheet after the thermofixation under 50-320 ℃ and 3MPa pressure.
The second-order transition temperature that records this veneer sheet is greater than 400 ℃ (adopting the DMA method to measure), and flexural strength is greater than 1500MPa, and modulus in flexure is greater than 110GPa, and interlaminar shear strength is greater than 75MPa.
The performance of the preparation of embodiment 9, polyimide resin and resin mold casting die
1) 18 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 70 ℃ of reflux in 20 mass parts methyl alcohol was obtained norbornylene diformate mono ester solution (NE) in 1 hour.
2) with 34 mass parts compd As
168 ℃ of reflux obtained compd A in 4 hours in 39 mass parts methyl alcohol
1Carboxylate solution, with 7 mass parts compd Bs
267 ℃ of reflux obtained compd B in 3 hours in 8 mass parts methyl alcohol
2Carboxylate solution.
3) with 30 mass parts 4,4 '-diaminodiphenyl oxide, 15 mass parts 4,4 '-diaminodiphenylmethane are dissolved in 34 parts of methyl alcohol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
2Carboxylate solution, stirred 10 hours down at 40 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1650, m is 2.11 among the formula I, n is 0.41.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 70 ℃/3h, 140 ℃/2h, 220 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 110Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 3MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 370 ℃ (adopting the DMA method to measure), and tensile strength is greater than 75MPa, and flexural strength is greater than 130MPa.
The performance of the preparation of embodiment 10, polyimide resin and resin mold casting die
1) 24 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 85 ℃ of reflux in 33 mass parts ethanol was obtained corresponding norbornylene diformate mono ester solution (NE) in 6 hours.
2) with 63 mass parts compd As
283 ℃ of reflux obtained compd A in 3 hours in 86 mass parts ethanol
2Carboxylate solution, with 6 mass parts compd Bs
386 ℃ of reflux obtained compd B in 5 hours in 9 mass parts ethanol
3Carboxylate solution.
3) with 16 mass parts mphenylenediamines, 32 mass parts 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 4-, 15 mass parts 3,4 '-diaminodiphenyl oxide is dissolved in the 60 mass parts ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
2And B
3Carboxylate solution, stirred 3 hours down at 20 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1940, m is 2.64 among the formula I, n is 0.18.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 70 ℃/3h, 150 ℃/2h, 210 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 50Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 4MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 360 ℃ (adopting the DMA method to measure), and tensile strength is greater than 70MPa, and flexural strength is greater than 120MPa.
The performance of the preparation of embodiment 11, polyimide resin and resin mold casting die
1) 21 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 81 ℃ of reflux in 28 mass parts ethanol was obtained corresponding norbornylene diformate mono ester solution (NE) in 3 hours.
2) with 48 mass parts compd As
184 ℃ of reflux obtained compd A in 4 hours in 70 mass parts ethanol
1Carboxylate solution, with 9 mass parts compd Bs
182 ℃ of reflux obtained compd B in 3 hours in 12 mass parts ethanol
1Carboxylate solution.
3) with 39 part 1, two (4-amino-benzene oxygen) benzene of 3-, 13 part 3,4 '-diaminodiphenyl oxide, 19 part 1, two (4-amino-benzene oxygen) benzene of 4-are dissolved in the mixed solvent of 60 parts of ethanol and 15 parts of acetone, stir the NE, the compd A that add above-mentioned preparation after half an hour successively
1And B
1Carboxylate solution, stirred 7 hours down at 35 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 2150, m is 2.55 among the formula I, n is 0.44.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 80 ℃/3h, 140 ℃/2h, 200 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 75Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 350 ℃ (adopting the DMA method to measure), and tensile strength is greater than 75MPa, and flexural strength is greater than 120MPa.
The performance of the preparation of embodiment 12, polyimide resin and carbon fiber composite polyimide material veneer sheet
1) 14 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 86 ℃ of reflux in 18 mass parts ethanol was obtained corresponding norbornylene diformate mono ester solution (NE) in 4 hours.
2) with 42 mass parts compd As
382 ℃ of reflux obtained compd A in 3 hours in 53 mass parts ethanol
3Carboxylate solution, with 4 mass parts compd Bs
383 ℃ of reflux obtained compd B in 2 hours in 6 mass parts ethanol
3Carboxylate solution.
3) with 6 mass parts Ursol D, 11 mass parts 4,4 '-diaminodiphenylmethane, 24 mass parts 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl are dissolved in the 32 mass parts ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
3And B
3Carboxylate solution, stirred 9 hours down at 40 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 2290, m is 2.75 among the formula I, n is 0.21.
The resin solution that step 3) is obtained carries out compound preparation prepreg with carbon fiber on wrapping machine, prepreg is carried out cutting, shop layer, obtains carbon fiber composite polyimide material veneer sheet after the thermofixation under 50-320 ℃ and 3MPa pressure.
The second-order transition temperature that records this veneer sheet is greater than 370 ℃ (adopting the DMA method to measure), and flexural strength is greater than 1300MPa, and modulus in flexure is greater than 90GPa, and interlaminar shear strength is greater than 70MPa.
The performance of the preparation of embodiment 13, polyimide resin and resin mold casting die
1) 44 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 68 ℃ of reflux in 45 mass parts methyl alcohol was obtained norbornylene diformate mono ester solution (NE) in 1 hour.
2) with 100 mass parts compd As
169 ℃ of reflux obtained compd A in 4 hours in 105 mass parts methyl alcohol
1Carboxylate solution, with 1 mass parts compd B
267 ℃ of reflux obtained compd B in 3 hours in 1 mass parts methyl alcohol
2Carboxylate solution.
3) with 149 mass parts, 2,2 '-two trifluoromethyls-4,4 '-benzidine is dissolved in 130 parts of ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
2Carboxylate solution, stirred 8 hours down at 35 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 2080, m is 2.54 among the formula I, n is 0.02.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 60 ℃/3h, 140 ℃/2h, 220 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 130Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 3MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 360 ℃ (adopting the DMA method to measure), and tensile strength is greater than 70MPa, and flexural strength is greater than 120MPa.
The performance of the preparation of embodiment 14, polyimide resin and resin mold casting die
1) 5 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 69 ℃ of reflux in 6 mass parts methyl alcohol was obtained norbornylene diformate mono ester solution (NE) in 3 hours.
2) with 80 mass parts compd As
167 ℃ of reflux obtained compd A in 5 hours in 78 mass parts methyl alcohol
1Carboxylate solution, with 20 mass parts compd Bs
368 ℃ of reflux obtained compd B in 4 hours in 25 mass parts methyl alcohol
3Carboxylate solution.
3) with 24 mass parts mphenylenediamines, 23 mass parts 3,4 '-diaminodiphenyl oxide is dissolved in 45 parts of methyl alcohol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
3Carboxylate solution, stirred 8 hours down at 30 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 8950, m is 17.85 among the formula I, n is 2.95.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 60 ℃/3h, 150 ℃/2h, 200 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 2300Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 3MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 350 ℃ (adopting the DMA method to measure), and tensile strength is greater than 80MPa, and flexural strength is greater than 120MPa.
The performance of the preparation of embodiment 15, polyimide resin and resin mold casting die
1) 80 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 83 ℃ of reflux in 110 mass parts ethanol was obtained norbornylene diformate mono ester solution (NE) in 3 hours.
2) with 95 mass parts compd As
185 ℃ of reflux obtained compd A in 4 hours in 125 mass parts ethanol
1Carboxylate solution, with 5 mass parts compd Bs
282 ℃ of reflux obtained compd B in 4 hours in 8 mass parts ethanol
2Carboxylate solution.
3) with 55 mass parts 4,4 '-diaminodiphenyl oxide, 55 mass parts 3,4 '-diaminodiphenyl oxide is dissolved in 105 parts of ethanol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
1And B
2Carboxylate solution, stirred 6 hours down at 25 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 1130, m is 1.33 among the formula I, n is 0.07.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 80 ℃/3h, 140 ℃/2h, 200 ℃/1h intensification thermal treatment, and recording its minimum melt viscosity is 45Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 360 ℃ (adopting the DMA method to measure), and tensile strength is greater than 50MPa, and flexural strength is greater than 110MPa.
The performance of the preparation of embodiment 16, polyimide resin and resin mold casting die
1) 24 mass parts end-capping reagent norbornylene dicarboxylic acid anhydrides, 69 ℃ of reflux in 20 mass parts methyl alcohol was obtained norbornylene diformate mono ester solution (NE) in 3 hours.
2) with 75 mass parts compd As
268 ℃ of reflux obtained compd A in 4 hours in 85 mass parts methyl alcohol
2Carboxylate solution, with 25 mass parts compd Bs
368 ℃ of reflux obtained compd B in 4 hours in 26 mass parts methyl alcohol
3Carboxylate solution.
3) with 20 mass parts mphenylenediamines, 10 mass parts 3,4 '-diaminodiphenyl oxide is dissolved in 35 parts of methyl alcohol, and stirring adds NE, the compd A of above-mentioned preparation successively after half an hour
2And B
3Carboxylate solution, stirred 6 hours down at 20 ℃, obtain the homogeneous phase solution of polyimid-base resin, calculating number-average molecular weight is 2150, m is 3.15 among the formula I, n is 0.77.
The resin solution that step 3) is obtained obtains the resin mold molding powder successively through 60 ℃/3h, 140 ℃/2h, 200 ℃/Ih intensification thermal treatment, and recording its minimum melt viscosity is 170Pa.s; This molding powder is obtained the virgin resin molding after thermofixation under 250-320 ℃ and the 2MPa pressure, the second-order transition temperature of this resin mold casting die is greater than 350 ℃ (adopting the DMA method to measure), and tensile strength is greater than 60MPa, and flexural strength is greater than 110MPa.
Claims (10)
1. general structure is suc as formula the polyimide resin shown in the I,
(formula I)
Among the formula I,
R
2=
-O-, or
Described m=1-20, n=0.01-6.
2. polyimide resin according to claim 1 is characterized in that: the number-average molecular weight of described polyimide resin is 1000-9000.
3. method for preparing the polyimide resin shown in the described formula I of claim 1 may further comprise the steps:
1) end-capping reagent and organic fatty alcoholic solvent are carried out esterification, obtain end-capping reagent list acid monoester solution;
2) aromatic series tetracarboxylic dianhydride and organic fatty alcoholic solvent are carried out esterification, obtain aromatic series tetracid two ester solutions;
3) aromatic diamine is dissolved in the organic fatty alcoholic solvent, adds end-capping reagent list acid monoester solution, the step 2 of step 1) then successively) aromatic series tetracid two ester solutions react, obtain the polyimide resin solution shown in the formula I;
Wherein, described end-capping reagent is the compound shown in the formula II,
(formula II);
Described aromatic series tetracarboxylic dianhydride is the mixture of following aromatic series tetracarboxylic dianhydride I and aromatic series tetracarboxylic dianhydride II, and wherein, the ratio of quality and the number of copies of aromatic series tetracarboxylic dianhydride I and aromatic series tetracarboxylic dianhydride II is 100: 1-30;
Described aromatic series tetracarboxylic dianhydride I is selected from shown in following formula A1, formula A2, the formula A3 a kind of in the compound:
Formula A1 formula A2 formula A3
Described aromatic series tetracarboxylic dianhydride II is selected from shown in following formula B1, formula B2, the formula B3 a kind of in the compound:
Formula B1 formula B2 formula B3
Described aromatic diamine is selected from a kind of in the following compound:
The ratio of quality and the number of copies of described end-capping reagent, aromatic series tetracarboxylic dianhydride and aromatic diamine is followed successively by 5-80: 100: 30-150.
4. method according to claim 3 is characterized in that: the temperature of reaction of reacting described in the step 3) is 5-40 ℃, and the reaction times is 1-10 hour.
5. according to claim 3 or 4 described methods, it is characterized in that: step 1), step 2) and step 3) described in the organic fatty alcoholic solvent be at least a in the following alcohol: methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol and the trimethyl carbinol; Or be the arbitrary proportion blended mixture of a kind of and following at least a solvent in the above-mentioned alcohol: acetone, tetrahydrofuran (THF), dioxane, benzene, toluene, chloroform and methylene dichloride.
6. method according to claim 3 is characterized in that: the ratio of quality and the number of copies of end-capping reagent described in the step 1) and organic fatty alcoholic solvent is 5-60: 5-600; Esterification described in the step 1) is carried out under the condition of 65-140 ℃ of reflux, and the reaction times is 1-6 hour.
7. method according to claim 3 is characterized in that: step 2) described in the ratio of quality and the number of copies of aromatic series tetracarboxylic dianhydride and organic fatty alcoholic solvent be 100: 60-1200; Step 2) esterification described in is carried out under the condition of 65-140 ℃ of reflux, and the reaction times is 1-6 hour.
8. method according to claim 3 is characterized in that: the ratio of quality and the number of copies of aromatic diamine described in the step 3) and organic fatty alcoholic solvent is 30-150: 10-800.
9. method according to claim 3 is characterized in that: described method comprises that also the polyimide resin solution that step 3) is obtained heat-treats, and obtains the step of solid polyimide resin.
10. the application of the polyimide resin shown in the described formula I of claim 1 in preparation polyimide resin based composites.
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| CN102181152A (en) * | 2011-03-30 | 2011-09-14 | 同济大学 | Preparation method for multidimensional mixed composite mateial of carbon fiber/polyimide resin modified by carbon nano tube |
| EP2876129B1 (en) * | 2013-11-25 | 2021-05-12 | Samsung Electronics Co., Ltd. | Composition for preparing polyimide, polyimide, and article including same |
| KR102276288B1 (en) | 2013-11-25 | 2021-07-12 | 삼성전자주식회사 | Composition of preparing polyimide, polyimide, article includong same, and display device |
| CN103740104B (en) * | 2013-12-27 | 2016-08-17 | 上海市合成树脂研究所 | The preparation method of securing member composite polyimide material |
| CN104151823B (en) * | 2014-09-02 | 2019-02-26 | 长春聚明光电材料有限公司 | Kapton and preparation method thereof |
| CN105037725A (en) * | 2015-07-13 | 2015-11-11 | 长春理工大学 | Polyimide oligomer, and preparation method and application thereof |
| CN105061764B (en) * | 2015-09-02 | 2018-03-02 | 中国科学院化学研究所 | A kind of thermoset polyimide resin and its composite laminate and their preparation method and application |
| CN105860443A (en) * | 2016-06-22 | 2016-08-17 | 北京飞箭基石科技有限公司 | Stratosphere carbon fiber prepreg development scheme |
| CN110541174B (en) * | 2018-05-28 | 2021-11-12 | 丰田自动车株式会社 | Polyimide/carbon fiber cloth water decomposition oxygen generation electrode and preparation method thereof |
| CN109337428A (en) * | 2018-10-17 | 2019-02-15 | 陕西航空电气有限责任公司 | A kind of fire resistant polyimide insulating impregnating varnish and its preparation method and application |
| CN109880091A (en) * | 2019-02-26 | 2019-06-14 | 中国科学院化学研究所 | A kind of semi-aromatic thermoset polyimide resin and preparation method thereof and purposes |
| CN111923441B (en) * | 2020-08-26 | 2022-10-11 | 中国航空工业集团公司济南特种结构研究所 | Preparation method of high-temperature-resistant polyimide resin-based composite material |
| CN114262315A (en) * | 2021-12-22 | 2022-04-01 | 山东非金属材料研究所 | Soluble norbornene-terminated imide oligomer and preparation method thereof |
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