CN101602856A - Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes - Google Patents
Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes Download PDFInfo
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- CN101602856A CN101602856A CNA2009100897730A CN200910089773A CN101602856A CN 101602856 A CN101602856 A CN 101602856A CN A2009100897730 A CNA2009100897730 A CN A2009100897730A CN 200910089773 A CN200910089773 A CN 200910089773A CN 101602856 A CN101602856 A CN 101602856A
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Abstract
The invention provides a kind of polyimide resin that can finish thermofixation reaction under lower temperature, its structure is as with shown in the following formula I: wherein, and R
1, R
2, R
3, R
4And R
5Be hydrogen (H), fluorine (F), trifluoromethyl (CF at the same time or separately
3), methyl (CH
3), ethyl (CH
2CH
3), methoxyl group (OCH
3), phenyl (Ph) or phenoxy group (OPh) wherein any one; R
1' be the group that m aromatic diamine molecule forms; R
2' make the group of its both sides directly link to each other or R for vacancy
2' be the group that n aromatic series tetracarboxylic dianhydride molecule forms; Wherein, m is selected from an integer of 1～11, and n is selected from an integer of 1～10.The present invention also provides the preparation method of the polyimide resin of this kind terminated with phenylacetylene anhydride naphthalene groups.The polyimide resin of terminated with phenylacetylene anhydride naphthalene groups provided by the invention has important use at high-technology fields such as Aeronautics and Astronautics, space technologies and is worth.
Description
Technical field
The present invention relates to a kind of polyimide resin and preparation method thereof and purposes of terminated with phenylacetylene anhydride naphthalene groups.
Background technology
Polyimide resin has over-all propertieies such as excellent heat-resisting, mechanics, electricity, is widely used at high-technology fields such as Aeronautics and Astronautics, space, microelectronics, precision optical machinery, medicine equipments.Polyimide resin mainly comprises thermoset and thermoplasticity two big classes, wherein thermoset polyimide resin has than higher temperature classification of thermoplastic polyimide resin and good processing characteristics, and excellent mechanical property, therefore can be used as the matrix resin of polymer matrix composites and adhesive application in structure/aggregated(particle) structure parts of making the Aeronautics and Astronautics aircraft.
In recent years, be subjected to people's attention with the end capped thermoset polyimide resin of phenylacetylene base phthalic anhydride owing to its good processing characteristics and resistance to elevated temperatures.United States Patent (USP) (U.S.Pat.5681967) discloses the end capped polyimide resin of phenylacetylene base phthalic anhydride, and this resin has good building-up properties, and the melt-processed window of resin is above 80 ℃.The end capped polyimide resin of phenylacetylene base phthalic anhydride has good fluidity of molten, solidify the thermosetting resin that the back forms through high-temperature cross-linking and have good resistance toheat, chemical resistance and wet-hot aging performance, so become one of the research focus in fire resistant polyimide material field in recent years.Chemical structure and molecular weight by the control resin can make the end capped polyimide resin of phenylacetylene base phthalic anhydride have very low melt viscosity, enable to be suitable for resin transfer moulding (RTM) machine-shaping continuous fibre enhancement resin based composites.Adopt RTM technology not only can obviously enhance productivity, reduce manufacturing cost, and can make the composite product of high quality, complex construction.Thereby, the polyimide resin that contains phenylacetylene base of the many RTM of being suitable for technologies is disclosed in recent years.For example, it is END CAPPED GROUP with phenylacetylene phthalic anhydride group that United States Patent (USP) (U.S.Pat.6359107) discloses a series of, by flexible aromatic diamine mixture and 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) or 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydride aromatic series such as (6FDA) dianhydride polymerization and the polyimide resin that obtains; It is END CAPPED GROUP that United States Patent (USP) (U.S.Pat.6911519) discloses with phenylacetylene phthalic anhydride group, by 3,3 ', 4,4 '-BPDA (s-BPDA) and the various flexible hybrid aromatic diamine combinations that contain ehter bond are through the polyimide resin that is suitable for RTM technology of high-temperature polycondensation reaction formation.These resins have very low melt viscosity and good melt stability thereof, are applicable to adopt RTM technology to make carbon fiber enhancement resin base composite material.
But, the polyimide resin that contains phenylacetylene phthalic anhydride group need be realized the thermofixation reaction of phenylacetylene group usually under the high temperature more than 370 ℃, to form thermoset polyimide resin, this RTM moulding process to fiber-reinforced resin matrix compound material has brought very big difficulty; Therefore, it is significant that development can be finished the polyimide resin of thermofixation at a lower temperature.
Summary of the invention
Main purpose of the present invention provides a kind of polyimide resin that can finish the thermofixation reaction under lower temperature.
Polyimide resin provided by the invention is the polyimide resin of the terminated with phenylacetylene anhydride naphthalene groups of formula I structure,
Formula I
Wherein, R
1, R
2, R
3, R
4And R
5Be hydrogen (H), fluorine (F), trifluoromethyl (CF at the same time or separately
3), methyl (CH
3), ethyl (CH
2CH
3), methoxyl group (OCH
3), phenyl (Ph) or phenoxy group (OPh) wherein any one; R
1' be the group that m aromatic diamine molecule forms; R
2' make the group of its both sides directly link to each other or R for vacancy
2' be the group that n aromatic series tetracarboxylic dianhydride molecule forms; Wherein, m is selected from an integer of 1～11, and n is selected from an integer of 1～10.
Wherein, described aromatic diamine can be for being selected from 3,4 ' diaminodiphenyl oxide (3,4 '-ODA), 4,4 ' diaminodiphenyl oxide (4,4 '-ODA), 1, two (4-amino-benzene oxygen) benzene (1,3 of 3-, 4-APB), 1, two (4-amino-benzene oxygen) benzene of 4-(1,4,4-APB), 4,4 ' diaminodiphenylmethane (MDA), 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene (6F-APB), 4,4 '-two (4-amino-benzene oxygen) biphenyl (BAB), 4,4 '-two (4-ammonia amido-2-4-trifluoromethylphenopendant) biphenyl (6F-BAB), 4,4 '-diamino-2,2 '-trifluoromethyl-biphenyl (TFDB), x kind in Ursol D (p-PDA) and the mphenylenediamine (m-PDA), wherein, x is a positive integer that is not more than m.
Preferably, R
2' be the group that n aromatic series tetracarboxylic dianhydride molecule forms, described aromatic series tetracarboxylic dianhydride is for being selected from 3,3 ', 4,4 '-BPDA (s-BPDA), 2,3,3 ', 4 '-BPDA (α-BPDA), 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) and 1,2,4, y kind in the 5-benzene tetracarboxylic acid acid anhydride (PMDA), wherein, y is selected from 1～6 and be not more than the integer of n.
The structural formula of the group that each aromatic diamine of more than enumerating and each aromatic series tetracarboxylic dianhydride form with unit molecule respectively is as follows:
The present invention also provides a kind of preparation method of polyimide resin of terminated with phenylacetylene anhydride naphthalene groups, operation steps is as follows: the aromatic diamine with 1～11 molar part under the nitrogen protection condition joins in the organic solvent, after treating that aromatic diamine dissolves fully, the aromatic series tetracarboxylic dianhydride of 0～10 molar part is joined in the organic solvent (when the aromatic series tetracarboxylic dianhydride is 0 molar part, mean and do not add the aromatic series tetracarboxylic dianhydride), reacted under the room temperature 1～10 hour; Add the phenylacetylene base naphthalene acid anhydride shown in the formula II of 2 molar part then as end-capping reagent;
Formula II
Wherein, R
1, R
2, R
3, R
4And R
5Be hydrogen (H), fluorine (F), trifluoromethyl (CF at the same time or separately
3), methyl (CH
3), ethyl (CH
2CH
3), methoxyl group (OCH
3), phenyl (Ph) or phenoxy group (OPh) wherein any one;
Aromatic diamine, aromatic series tetracarboxylic dianhydride and the weight content of phenylacetylene base naphthalene acid anhydride in solution are 5～60%; Reaction system is warming up to 30～150 ℃ and continues reaction 1～10 hour, obtains the organic solution of the prepolymer of polyamic acid; The inertia aromatic solvent is added in the polyamic acid prepolymer organic solution, adopt division box elevated temperature backflow simultaneously band water, carry out imidization; After waiting to no longer include water and being taken out of, further elevated temperature is isolated most of inertia aromatic solvent; Reaction soln is sunk in the inert solvent, obtain throw out, behind the thorough washing, dry sediment promptly gets the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups.
Described organic solvent is preferably non-proton polar organic solvent, for example can be N, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP) and meta-cresol.
Described aromatic diamine can be 3,4 ' diaminodiphenyl oxide (3,4 '-ODA), 4,4 ' diaminodiphenyl oxide (4,4 '-ODA), 1, two (4-amino-benzene oxygen) benzene (1 of 3-, 3,4-APB), 1, two (4-amino-benzene oxygen) benzene of 4-(1,4,4-APB), 4,4 ' diaminodiphenylmethane (MDA), 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene (6F-APB), 4,4 '-two (4-amino-benzene oxygen) biphenyl (BAB), 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl (6F-BAB), 4,4 '-diamino-2,2 '-trifluoromethyl-biphenyl (TFDB), wherein a kind of or wherein several mixture that mixes by arbitrary proportion of Ursol D (p-PDA) and mphenylenediamine (m-PDA).
Described aromatic series tetracarboxylic dianhydride can be 3,3 ', 4,4 '-BPDA (s-BPDA), 2,3,3 ', 4 '-BPDA (α-BPDA), 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 3,3 ', 4, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of 4 '-benzophenone tetracarboxylic dianhydride (BTDA) and 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA).
Described inertia aromaticity solvent can be toluene, 1,3-dimethylbenzene, 1,4-dimethylbenzene, 1,3-diethylbenzene, 1, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of what 1-methyl-2-ethylbenzene of 4-diethylbenzene.
Described inert solvent can be wherein a kind of or wherein several mixture that mixes by arbitrary proportion of water, methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, tetrahydrofuran (THF), dioxane.
The polyimide resin of terminated with phenylacetylene anhydride naphthalene groups provided by the invention has important use at high-technology fields such as Aeronautics and Astronautics, space technologies and is worth, and prepared composite product can use under the high temperature more than 320 ℃.Illustrate its application method below: with carbon fiber or fiberglass braided precast body, put into airtight mould then, heating and melting is formed low viscous melt, inject mould then; Solidified 1～2 hour mold heated to 310～370 ℃ that will inject the polyimide resin of described terminated with phenylacetylene anhydride naphthalene groups at last, and cooling back die sinking obtains the carbon fiber enhancement resin base composite material product.
The heat curing temperature of the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups provided by the invention hangs down 1-60 ℃ than the polyimide resin of phenylacetylene phthalic anhydride group end capping, and the thermoset polyimide resin that forms after the thermofixation has good resistance toheat.Simultaneously, the polyimide resin of described terminated with phenylacetylene anhydride naphthalene groups has good melting behaviour, and its molten resin has low melt viscosity and good viscosity stability.
Embodiment
Embodiment 1
With 3, (3,4 '-ODA) 400.28g joins in the 5000ml N-N-methyl-2-2-pyrrolidone N-(NMP) 4 ' diaminodiphenyl oxide, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 294.22g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 4 hours under the room temperature.With 596.58g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 130 ℃ reaction 5 hours.After adding 700ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 180 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 8000ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 vacuum-drying.Productive rate is 96.1%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 356 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 8.2Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 13.4Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 346 ℃ through 350 ℃ of curing, and the initial decomposition temperature of resin is 467 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 2
Ursol D (p-PDA) 108.84g mphenylenediamine (m-PDA) 108.84g is joined in the 3800ml N-N-methyl-2-2-pyrrolidone N-(NMP), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 310.21g 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) stirred 10 hours under the room temperature.With 596.58g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 5 hours.Add 650ml 1, behind the 4-diethylbenzene, adopt division box, be heated to 1,4-diethyl refluxing toluene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 4-diethyl toluene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 7700ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 98.0%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 335 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 9.5Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 24.3Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 368 ℃ through 330 ℃ of curing, and the initial decomposition temperature of resin is 517 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 3
With 1, two (4-amino-benzene oxygen) benzene (1 of 3-, 3,4-APB) 584.66g joins 5300ml N, dinethylformamide (DMF) stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 444.27g 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) stirred 1 hour under the room temperature.With 596.58g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 8 hours.Add 800ml 1, behind the 4-toluene, adopt division box, be heated to 1, the 4-refluxing toluene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 4-toluene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 8000ml Virahol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 95.6%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 351 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 5.5Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 14.3Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 347 ℃ through 350 ℃ of curing, and the initial decomposition temperature of resin is 469 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 4
With 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene (6F-APB) 100.88g joins in the 600ml meta-cresol, stirs under the nitrogen atmosphere condition, treat to dissolve fully the back and add 31.02g 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) stirred 9 hours under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 130 ℃ reaction 2 hours.After adding 100ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 180 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1200ml dioxane precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 97.3%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 347 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 5.1Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 12.8Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 356 ℃ through 350 ℃ of curing, and the initial decomposition temperature of resin is 487 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 5
With 4,4 ' diaminodiphenylmethane (MDA) 39.65g joins 500ml N,N-dimethylacetamide (DMAc), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 29.42g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 10 hours under the room temperature.With 71.67g 4-(3,5-two phenoxy groups, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 140 ℃ reaction 2 hours.Add 50ml 1, behind the 3-dimethylbenzene, adopt division box, be heated to 1, the 3-refluxing xylene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, elevated temperature steams most ofly 1, behind the 3-dimethylbenzene, stops heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1200ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 97.7%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 334 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 7.2Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 17.3Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 341 ℃ through 330 ℃ of curing, and the initial decomposition temperature of resin is 435 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 6
Ursol D (p-PDA) 166.44g mphenylenediamine (m-PDA) 51.24g is joined in the 3400ml N-N-methyl-2-2-pyrrolidone N-(NMP), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 322.23g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) stirred 2 hours under the room temperature.With 596.58g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 110 ℃ reaction 6 hours.After adding 800ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 170 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 9900ml Virahol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 96.6%.
Resulting resin is tested by DSC, and its thermofixation peak temperature is 338 ℃; Through dynamic rheological property test, resin melt viscosity is minimum to be 17.9Pas, in 280 ℃ of constant temperature after 1 hour resin melt viscosity be 26.3Pas; After 1 hour, the second-order transition temperature that solidifies the back resin is 363 ℃ through 340 ℃ of curing, and the initial decomposition temperature of resin is 521 ℃ after thermogravimetic analysis (TGA) (TGA) test is solidified.
Embodiment 7
With Ursol D (p-PDA) 10.88g 1, two (the 4-amido phenoxy group) benzene (1 of 3-, 3,4-APB) 29.23g joins in the 450ml meta-cresol, stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 29.42g 3,3 ', 4,4 '-BPDA (s-BPDA) stirred 10 hours under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 6 hours.After adding 100ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 190 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 900ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 95.7%.
Embodiment 8
(4,4 '-ODA) 20.02g joins in the 410ml meta-cresol with Ursol D (p-PDA) 10.88g 4,4 ' diaminodiphenyl oxide, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 29.42g 3,3 ', 4,4 '-BPDA (s-BPDA) stirred 3 hours under the room temperature.With 73.56g 4-(2-trifluoromethyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 reaction 1 hour.Add 70ml 1, behind the 4-diethylbenzene, adopt division box, be heated to 1, the 4-diethylbenzene refluxes, and progressively takes the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 4-diethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 800ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 98.1%.
Embodiment 9
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 20.01g, (4,4 '-ODA) 20.02g joins in the 630ml meta-cresol 4,4 ' diaminodiphenyl oxide, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 14.72g 3,3 ', 4,4 '-BPDA (s-BPDA) and 14.72g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 7 hours under the room temperature.With 63.26g 4-(2-fluorine, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 130 ℃ reaction 1 hour.Add 90ml 1, behind the 3-diethylbenzene, adopt division box, be heated to 1, the 3-diethylbenzene refluxes, and progressively takes the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 3-diethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 800ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 95.1%.
Embodiment 10
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 80.06g, 1, (1,3,4-APB) 467.73g joins in the 2500ml N-N-methyl-2-2-pyrrolidone N-(NMP) two (4-amino-benzene oxygen) benzene of 3-, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 294.22g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 8 hours under the room temperature.With 596.58g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 140 ℃ reaction 9 hours.After adding 160ml 1-methyl-2-ethylbenzene, adopt division box, be heated to 1-methyl-2-ethylbenzene and reflux, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, heat up steam most of 1-methyl-2-ethylbenzene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 3500ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 96.6%.
Embodiment 11
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 80.06g, 1, two (the 4-amido phenoxy group) benzene (1,3 of 3-, 4-APB) 467.73g joins 1500ml N, in the dinethylformamide (DMF), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 294.22g 3,3 ', 4,4 '-BPDA (s-BPDA) stirred 2 hours under the room temperature.With 596.58g 4-(3-trifluoromethyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 130 ℃ reaction 6 hours.After adding 160ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, heat up steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 3500ml tetrahydrofuran (THF) precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 94.6%.
Embodiment 12
51.24g joins 2300ml N with Ursol D (p-PDA) 166.44g mphenylenediamine (m-PDA), in the N-N,N-DIMETHYLACETAMIDE (DMAc), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 147.11g 3,3 ', 4,4 '-BPDA (s-BPDA) and 147.11g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 6 hours under the room temperature.With 868.58g 4-(3,5-bis trifluoromethyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.After adding 1800ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 170 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 5000ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 94.7%.
Embodiment 13
With 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) benzene (6F-APB) 100.84g joins in the 600ml meta-cresol, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 14.72g 3,3 ', 4,4 '-BPDA (s-BPDA) and 14.72g2,3,3 ', 4 '-BPDA (α-BPDA), stirred 10 hours under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 2 hours.Add 100ml 1, behind the 3-dimethylbenzene, adopt division box, be heated to 1, the 3-refluxing xylene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 3-dimethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1200ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 95.3%.
Embodiment 14
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 20.01g, 4,4 ' diaminodiphenyl oxide (4,4 '-ODA) 20.02g joins 630ml N, in the N-N,N-DIMETHYLACETAMIDE (DMAc), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 44.42g4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) stirred 3 hours under the room temperature.With 74.88g 4-(3-phenyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 6 hours.After adding 110ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 120-150 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1800ml Virahol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 97.1%.
Embodiment 15
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 80.06g, 1, two (the 4-amido phenoxy group) benzene (1 of 3-, 3,4-APB) 467.73g joins in the 1900ml N-N-methyl-2-2-pyrrolidone N-(NMP), stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 444.24g 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) stirred 5 hours under the room temperature.With 624.64g 4-(3-methyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 3 hours.After adding 200ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 170-190 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 3500ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 96.0%.
Embodiment 16
With 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene (6F-APB) 100.84g joins in the 600ml meta-cresol, stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 44.42g 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) stirred 1 hour under the room temperature.With 65.66g 4-(3-phenoxy group, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.After adding 170ml1-methyl-2-ethylbenzene, adopt division box, be heated to 1-methyl-2-ethylbenzene and reflux, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, behind the most of 1-methyl-2-ethylbenzene that heats up, stop heating.Reaction solution naturally cools to room temperature.Pour reaction solution into 1000ml and remove ethanol sedimentation, the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 94.9%.
Embodiment 17
With 4,4 '-two (4-amino-benzene oxygen) biphenyl (BAB) 100.83g joins in the 300ml meta-cresol, stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 21.82g 1,2,4, and 5-benzene tetracarboxylic acid acid anhydride (PMDA) stirred 1 hour under the room temperature.With 72.47g 4-(4-ethyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.Add 120ml1, behind the 3-dimethylbenzene, adopt division box, be heated to 1, the 3-refluxing xylene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 3-dimethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1100ml Virahol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 97.7%.
Embodiment 18
With 4,4 '-diamino-2,2 '-trifluoromethyl-biphenyl (TFDB) 64.05g joins in the 100ml meta-cresol, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 44.42g 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA), stirred 1 hour under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.After adding 160ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 180 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 900ml deionized water precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 97.3%.
Embodiment 19
With 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl (6F-BAB) 100.83g joins 200ml N, in the N-N,N-DIMETHYLACETAMIDE (DMAc), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 44.42g 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides (6FDA) stirred 1 hour under the room temperature.With 78.08g 4-(3-phenoxy group, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 130 ℃ reaction 7 hours.Add 130ml 1, behind the 3-dimethylbenzene, adopt division box, be heated to 1, the 3-refluxing xylene is progressively taken the moisture in the reaction system out of, carries out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 3-dimethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1200ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 94.2%.
Embodiment 20
With 1, and two (the 4-amido phenoxy group) benzene of 4-(1,4,4-APB) 584.66 join in the 300ml N-N-methyl-2-2-pyrrolidone N-(NMP), under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 44.42g 3,3 ', 4,4 '-BPDA (s-BPDA) stirred 1 hour under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.After adding 160ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, heat up steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1000ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 96.3%.
Embodiment 21
With 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl (6F-BAB) 58.42g joins in the 500ml meta-cresol, stirs under the nitrogen atmosphere condition, treat to dissolve fully the back and add 29.42g 3,3 ', 4, stirred 1 hour under 4 '-BPDA (s-BPDA) room temperature.With 65.27g 4-(3,5-dimethyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.Add 130ml 1, behind the 4-dimethylbenzene, adopt division box, be heated to backflow, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, heat up that it is most of 1 to steam, behind the 4-dimethylbenzene, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1600ml methyl alcohol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 95.7%.
Embodiment 22
With 1, (1,4,4-APB) 58.47g joins in the 330ml meta-cresol two (the 4-amido phenoxy group) benzene of 4-, stirs under the nitrogen atmosphere condition, treats to dissolve fully the back and adds 21.82g 1,2,4, and 5-benzene tetracarboxylic acid acid anhydride (PMDA) stirred 1 hour under the room temperature.With 59.66g 4-(1-phenylacetylene base) 1,8-naphthalene acid anhydride (PENA) adds in the reaction soln, elevated temperature to 150 ℃ reaction 7 hours.After adding 100ml toluene, adopt division box, be heated to refluxing toluene, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, be warming up to 180 ℃, steam most of toluene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 1000ml tetrahydrofuran (THF) precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 98.1%.
Embodiment 23
With 3,4 ' diaminodiphenyl oxide (3,4 '-ODA) 80.06g, 1, (1,3,4-APB) 467.73g joins in the 2500ml N-N-methyl-2-2-pyrrolidone N-(NMP) two (4-amino-benzene oxygen) benzene of 3-, under the nitrogen atmosphere condition, stir, treat to dissolve fully the back and add 294.22g 2,3,3 ', 4 '-BPDA (α-BPDA), stirred 8 hours under the room temperature.With 780.78g 4-(3-phenyl, 1-phenylacetylene base) 1,8-naphthalene acid anhydride adds in the reaction soln, elevated temperature to 140 ℃ reaction 9 hours.After adding 160ml 1-methyl-2-ethylbenzene, adopt division box, be heated to 1-methyl-2-ethylbenzene and reflux, progressively take the moisture in the reaction system out of, carry out imidization.When treating to no longer include in the division box water and taking out of, heat up steam most of 1-methyl-2-ethylbenzene after, stop heating.Reaction solution naturally cools to room temperature.Reaction solution poured in the 3500ml ethanol precipitate the thorough washing after-filtration.Powder after the filtration obtains polyimide resin after 100-220 ℃ of vacuum-drying.Productive rate is 96.6%.
Claims (10)
1, the polyimide resin of the terminated with phenylacetylene anhydride naphthalene groups of formula I structure,
Formula I
Wherein, R
1, R
2, R
3, R
4And R
5Be wherein any one of hydrogen, fluorine, trifluoromethyl, methyl, ethyl, methoxyl group, phenyl or phenoxy group at the same time or separately; R
1' be the group that m aromatic diamine molecule forms; R
2' make the group of its both sides directly link to each other or R for vacancy
2' be the group that n aromatic series tetracarboxylic dianhydride molecule forms; Wherein, m is selected from an integer of 1～11, and n is selected from an integer of 1～10.
2, the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups according to claim 1, it is characterized in that: described aromatic diamine is for being selected from 3,4 ' diaminodiphenyl oxide, 4,4 ' diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 ' diaminodiphenylmethane, 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (4-ammonia amido-2-4-trifluoromethylphenopendant) biphenyl, 4,4 '-diamino-2,2 '-trifluoromethyl-biphenyl, x kind in Ursol D and the mphenylenediamine, wherein, x is a positive integer that is not more than m.
3, the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups according to claim 1 is characterized in that: R
2' be the group that n aromatic series tetracarboxylic dianhydride molecule forms, described aromatic series tetracarboxylic dianhydride is for being selected from 3,3 ', 4,4 '-BPDA, 2,3,3 ', 4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides and 1,2,4, y kind in the 5-benzene tetracarboxylic acid acid anhydride, wherein, y is selected from 1～6 and be not more than the integer of n.
4, the preparation method of the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups, operation steps is as follows: the aromatic diamine with 1～11 molar part under the nitrogen protection condition joins in the organic solvent, after treating that aromatic diamine dissolves fully, the aromatic series tetracarboxylic dianhydride of 0～10 molar part is joined in the organic solvent, reacted under the room temperature 1～10 hour; Add the phenylacetylene base naphthalene acid anhydride shown in the formula II of 2 molar part then as end-capping reagent;
Formula II
Wherein, R
1, R
2, R
3, R
4And R
5Be wherein any one of hydrogen, fluorine, trifluoromethyl, methyl, ethyl, methoxyl group, phenyl or phenoxy group at the same time or separately;
Aromatic diamine, aromatic series tetracarboxylic dianhydride and the weight content of phenylacetylene base naphthalene acid anhydride in solution are 5～60%; Reaction system is warming up to 30～150 ℃ and continues reaction 1～10 hour, obtains the organic solution of the prepolymer of polyamic acid; The inertia aromatic solvent is added in the polyamic acid prepolymer organic solution, adopt division box elevated temperature backflow simultaneously band water, carry out imidization; After waiting to no longer include water and being taken out of, further elevated temperature is isolated most of inertia aromatic solvent; Reaction soln is sunk in the inert solvent, obtain throw out, behind the thorough washing, dry sediment promptly gets the polyimide resin of terminated with phenylacetylene anhydride naphthalene groups.
5, preparation method according to claim 4, it is characterized in that: organic solvent is N, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-and meta-cresol.
6, preparation method according to claim 4, it is characterized in that: aromatic diamine is 3,4 ' diaminodiphenyl oxide, 4,4 ' diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 ' diaminodiphenylmethane, 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (4-amino-2-4-trifluoromethylphenopendant) biphenyl, 4,4 '-diamino-2,2 '-trifluoromethyl-biphenyl, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of Ursol D and mphenylenediamine.
7, preparation method according to claim 4 is characterized in that: described aromatic series tetracarboxylic dianhydride is 3,3 ', 4,4 '-BPDA, 2,3,3 ', 4 '-BPDA, 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 4, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of 4 '-(hexafluoro sec.-propyl) two adjacent pyromellitic acid dianhydrides.
8, preparation method according to claim 4, it is characterized in that: described inertia aromaticity solvent is a toluene, 1,3-dimethylbenzene, 1,4-dimethylbenzene, 1,3-diethylbenzene, 1, wherein a kind of or wherein several mixture that mixes by arbitrary proportion of what 1-methyl-2-ethylbenzene of 4-diethylbenzene.
9, preparation method according to claim 4 is characterized in that: described inert solvent is wherein a kind of or wherein several mixture that mixes by arbitrary proportion of water, methyl alcohol, ethanol, propyl alcohol, Virahol, acetone, tetrahydrofuran (THF), dioxane.
10, the purposes of the polyimide resin of the described terminated with phenylacetylene anhydride naphthalene groups of claim 1, it is characterized in that: with carbon fiber or fiberglass braided precast body, put into airtight mould then, heating and melting is formed low viscous melt, inject mould then; Solidified 1～2 hour mold heated to 310～370 ℃ that will inject the polyimide resin of described terminated with phenylacetylene anhydride naphthalene groups at last, and cooling back die sinking obtains the carbon fiber enhancement resin base composite material product.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102634020A (en) * | 2011-09-19 | 2012-08-15 | 京东方科技集团股份有限公司 | Prepolymer, oriented film, preparation method for oriented film, and liquid crystal display device |
| CN106084222A (en) * | 2016-06-30 | 2016-11-09 | 杭州福斯特光伏材料股份有限公司 | Intrinsical height heat conduction polyimides containing polyacetylene chain structure and preparation method |
| KR101781706B1 (en) * | 2012-11-12 | 2017-09-25 | 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. | Aromatic imide compound and method for producing same |
| CN109370161A (en) * | 2018-11-22 | 2019-02-22 | 安徽汇创新材料有限公司 | A kind of preparation method of the glass toughening manure pit of corrosion-resistant cracking resistance |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
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2009
- 2009-07-23 CN CNA2009100897730A patent/CN101602856A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634020A (en) * | 2011-09-19 | 2012-08-15 | 京东方科技集团股份有限公司 | Prepolymer, oriented film, preparation method for oriented film, and liquid crystal display device |
| WO2013041017A1 (en) * | 2011-09-19 | 2013-03-28 | 京东方科技集团股份有限公司 | Prepolymer, oriented film and preparation method thereof, and liquid crystal display device |
| CN102634020B (en) * | 2011-09-19 | 2013-09-11 | 京东方科技集团股份有限公司 | Prepolymer, oriented film, preparation method for oriented film, and liquid crystal display device |
| KR101781706B1 (en) * | 2012-11-12 | 2017-09-25 | 에이제트 일렉트로닉 머티어리얼스 (룩셈부르크) 에스.에이.알.엘. | Aromatic imide compound and method for producing same |
| CN106084222A (en) * | 2016-06-30 | 2016-11-09 | 杭州福斯特光伏材料股份有限公司 | Intrinsical height heat conduction polyimides containing polyacetylene chain structure and preparation method |
| CN109370161A (en) * | 2018-11-22 | 2019-02-22 | 安徽汇创新材料有限公司 | A kind of preparation method of the glass toughening manure pit of corrosion-resistant cracking resistance |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
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