CN1123589C - Thermosetting polyimide base resin and its prepn. - Google Patents
Thermosetting polyimide base resin and its prepn. Download PDFInfo
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- CN1123589C CN1123589C CN 01118566 CN01118566A CN1123589C CN 1123589 C CN1123589 C CN 1123589C CN 01118566 CN01118566 CN 01118566 CN 01118566 A CN01118566 A CN 01118566A CN 1123589 C CN1123589 C CN 1123589C
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Abstract
The present invention discloses basal body resin of thermosetting polyimide, which is composed of the components of the following proportion by weight: 10 to 55 of reactive end capping, 100 of aromatic tetracid dianhydride and 35 to110 of aromatic diamine. The basal body resin can be used for a long term at 310 to 320 DEG C; the basal body resin has good shock resistance and is capable of obviously reducing a micro-crack phenomenon in the process of high-temperature use. The composite material of the resin of the present invention can be used for high-temperature resistant and corrosion resistant components and parts of which the use temperature of manufacture requirement reaches as high as 310 to 320 DEG C in the fields of aviation, spaceflight, precise machine and petrochemical industry.
Description
The present invention relates to a kind of thermoset polyimide resin and preparation method thereof.
Adopt the thermoset polyimide resin of PMR method preparation to have the favorable manufacturability energy.With carbon fiber enhancement resin base composite material specific tenacity height, the specific modulus height of this resinoid preparation, have excellent thermal oxidation resistance stability and high-temperature mechanics mechanical property.Wherein the most representative is the PMR-15 resin (U.S.Patent 3,745,149) of U.S. NASA development and the KH-304 resin of Institute of Chemistry, Academia Sinica's development.PMR-15 and KH-304 resin be by norbornylene list formic acid monoesters (NE), 3,3 ', 4,4 '-benzophenone, two acid diesters (BTDE) and 4, and 4 '-diaminodiphenylmethane (MDA) prepares in the low-boiling point alcohol kind solvent.Its difference is that it is solvent that PMR-15 adopts methyl alcohol, and it is main solvent that the KH-304 resin then adopts ethanol.By the carbon fiber enhancement resin base composite material of this class matrix resin preparation can be under 316 ℃ high temperature life-time service, be widely used in the high-temperature structural components of space flight, aviation aircraft.But there is an important disadvantages in this class matrix material, and promptly because the poor toughness of matrix resin causes matrix material to be easy to generate fine fisssure in the high temperature use, this has had a strong impact on its use properties.People such as R.H.Pater succeed in developing LaRC
TM-RP46 (Proc.of the Int ' 1.SAMPESymp.), it be with may be nontoxic 3, (3,4 '-ODA) replaces 4,4 '-two amido ditanes (MDA) among the PMR-15 and the PMR polyimide type resin made to 4 '-diamines yl diphenyl ether.In order to satisfy the more demand of elevated operating temperature, people such as T.T.Serafini (NASA TM X-71894; NASA-TM-88942) disclosing can be at 371 ℃ of s-generation PMR type polyimid-base resin (PMR-II-50) that use down, this resin is by 4, and 4 '-(hexafluoro sec.-propyl) two adjacent benzene list formic acid mono-methyls (6FDE), Ursol D (PDA) and three kinds of components of norbornylene list formic acid mono-methyl (NE) react in lower boiling methanol solution and generate.Because the costing an arm and a leg of 6FDE, and the content in resin big (accounting for the 70-80% of monomer total amount), therefore, the manufacturing cost of resin is very high, is difficult for extensive and a large amount of use.Except some special purposes, be difficult to widen Application Areas, this has limited its development to a great extent.
The object of the present invention is to provide a kind of can be at the thermosetting polyimide base resin of 310-320 ℃ of following life-time service, this resin raw material is easy to get, cost is lower, the solidify material that after solidifying, obtains (with PMR-15 relatively) have a good shock resistance.Therefore, carbon fiber enhancement resin base composite material prepared therefrom can obviously reduce the fine fisssure phenomenon in the high temperature use.
Another object of the present invention is to provide a kind of preparation method of thermosetting polyimide base resin.
A kind of thermosetting polyimide base resin of the present invention, in weight part, form by following component and content:
Reactive end-capping reagent 10-55
Aromatic series tetracarboxylic dianhydride 100
Aromatic diamine 35-110
Described reactive end-capping reagent means the organic compound with following chemical structure:
Described aromatic series tetracarboxylic dianhydride means organic compound and the isomer thereof with following chemical structure:
Described aromatic diamine is the mixture of aromatic diamine II or itself and aromatic diamine I.
Described aromatic diamine I means organic compound and the derivative thereof with following chemical structure:
Described aromatic diamine II means organic compound and the derivative thereof with following chemical structure:
The preparation method of a kind of thermosetting polyimide base resin of the present invention in weight part, follows these steps to carry out:
1. the reactive end-capping reagent of 10-55 part is refluxed in organic solvent and generate corresponding carboxylic acid monoesters solution (1);
2. 100 parts of aromatic series tetracarboxylic dianhydrides are refluxed in organic solvent and generate corresponding aroma family two acid diesters solution (2);
3. 35-110 part aromatic diamine is dissolved in the organic solvent, adds solution (1) and solution (2) then successively,, obtain substrate resin solution at 5-25 ℃ of following stirring reaction 1-7 hour;
4. substrate resin solution is adopted ordinary method to carry out thermofixation,, promptly get thermosetting polyimide base resin of the present invention as 50-350 ℃ of heat curing process moulding.
Described organic solvent can be ethanol, methyl alcohol, Virahol, propyl carbinol, N-Methyl pyrrolidone, N,N-dimethylacetamide or its mixture.
The consumption of the organic solvent of described reactions steps in 1. is preferably 5-800 part; The consumption of the organic solvent of described reactions steps in 2. is preferably 70-1400 part; The consumption of the organic solvent of described reactions steps in 3. is preferably 5-3000 part.
Thermosetting polyimide base resin of the present invention, the modest viscosity of its substrate resin solution, package stability is better than PMR-15; This resin solution is suitable for impregnation of carbon fibers, glass fibre or aramid fiber and makes the prepreg of excellent property (band or cloth); This prepreg can obtain the polymer matrix composites of porosity low (1-2%) after 50-350 ℃ heat curing process moulding, its every performance all meets or exceeds the level of PMR-15 resin.Table 1 is the fundamental property of typical heat solidity polyimide resin solution of the present invention.
The fundamental property of table 1. typical heat solidity polyimide resin solution
| Performance | Index |
| Outward appearance | Red homogeneous phase solution |
| Solids content (wt%) | 10-60 |
| Solvent | The low-boiling point alcohol kind solvent |
| 25 ℃ of viscosity | 15-1000c.p. |
| Package stability | Room temperature:〉2 months 4 ℃: 6 months |
Thermosetting polyimide base resin of the present invention is characterized in that adopting heat treatment process as shown in table 2 to prepare material prepreg or molding powder.
Typical polyimide molding powder of table 2. and carbon fibre reinforced composite
The heat treatment process of prepreg (in vacuum drying oven, carrying out)
| Temperature (℃) | The constant temperature treatment time (hour) |
| 50-80 | 0.5-4.0 |
| 70-100 | 0.5-4.0 |
| 100-130 | 0.5-8.0 |
| 140-160 | 0.5-8.0 |
| 200-240 | 0.5-10.0 |
Thermosetting polyimide base resin of the present invention is characterized in that adopting heat curing process process as shown in table 3 that prepreg or molding powder are prepared into composite product or sheet material.
The thermofixation molding process of typical Thermocurable polyimide virgin resin of table 3. and matrix material thereof
| Temperature (℃) | Pressure, time |
| 260-300 | Contact is pressed, 15-30min |
| 300-330 | 1-10MPa, 1-8 hour |
| 330-350 | Contact is pressed, 2-10 hour |
Thermosetting polyimide base resin of the present invention is characterized in that having typical heat performance and the mechanical property shown in the table 4 by the composite product of the preparation of the heat treatment process parameter shown in the table 3.
The thermal characteristics and the mechanical property of the typical polyimide thermofixation of table 4. virgin resin
| Performance | Index | |
| Resin * of the present invention | KH-304 | |
| Crosslinking temperature (℃) | 270-350 | 270-320 |
| Weightless 5% temperature (℃) | 498 | 440 |
| Weightless 10% temperature (℃) | 542 | 475 |
| Second-order transition temperature (℃) | 365 | 345 |
| At 320 ℃/latm/500hrs/N 2In weightlessness (%) | ＜4 | - |
| At 320 ℃, latm, the weightlessness among the 400hrs.air (%) | ＜6 | - |
| Flexural strength, MPa | ＞70 | 65 |
| Modulus in flexure, GPa | ＞8 | 8 |
| Tensile strength, MPa | ＞60 | 50-60 |
| Tensile modulus, GPa | ＞4 | 4 |
| Shock strength (non-notch), KJ/m 2 | ＞21 | 4.5 |
Resin * of the present invention is embodiment 1 a made resin
Thermoset polyimide resin of the present invention is characterized in that having the fundamental property shown in the table 5 by this matrix resin and continuous carbon fibre through the continuous carbon fibre enhanced polymer matrix composites of the moulding process of thermofixation shown in the table 3 preparation.These polymer matrix composites can be used for making the corrosion-and high-temp-resistant component that require the Aeronautics and Astronautics of use temperature up to 310-320 ℃, precision optical machinery, petrochemical industry.
The typical mechanical property of table 5 matrix material
| Performance | This staple fibre of index T-300//T-300/KH-304 invention resin * resin * of the present invention |
| Flexural strength, 316 ℃ of MPa room temperatures | 1500 120 1489 1050 80 840 |
| Modulus in flexure, 316 ℃ of GPa room temperatures | 116 9.0 115 105 7.5 104 |
| Interlaminar shear strength, 316 ℃ of MPa room temperatures | 116 110 105 65 |
| Porosity | ＜1-2％ ＜1-2％ 1-2％ |
| Second-order transition temperature (℃) DMA | 385-410 390 340-350 |
Resin * of the present invention is embodiment 1 a made resin
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1. takes by weighing the 183.690g compd B
1, the backflow esterification obtains compd B in the 336.2ml anhydrous methanol
1Carboxylate solution; Take by weighing the 78.797g compd A
1, the backflow esterification obtains compd A in the 97.3ml anhydrous methanol
1Carboxylate solution.Take by weighing the 44.993g Compound C
1With the 82.493g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 70.0ml anhydrous methanol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 4 hours, obtain homogeneous phase substrate resin solution solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.This veneer sheet has typical performance such as table 5.
Embodiment 2. takes by weighing the 187.744g compd B
1, the backflow esterification obtains compd B in the 494.1ml dehydrated alcohol
1Carboxylate solution; Take by weighing the 76.608g compd A
1, the backflow esterification obtains compd A in the 136.1ml dehydrated alcohol
1Carboxylate solution.Take by weighing the 60.452g Compound C
1With the 55.418g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 75.0ml dehydrated alcohol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 5 hours, obtain the homogeneous phase substrate resin solution.This resin solution 40-200 ℃ of temperature programming thermal treatment, is obtained the molding powder; This molding powder is through obtaining virgin resin molding (plate, piece) after the thermofixation under the pressure of 200-350 ℃ and 1-3.0MPa.The typical performance of this molding: T
g: 395 ℃; T
d: 550 ℃; Flexural strength: 70MPa; Tensile strength: 60MPa; Unnotched impact strength: 18KJ/m
2
Embodiment 3. takes by weighing 190.792 compd Bs
2, in the 240.1ml anhydrous methanol, reflux and obtain compd B
2Carboxylate solution; Take by weighing the 92.261g compd A
3, the backflow esterification obtains compd A in the 263.4ml propyl carbinol
3Carboxylate solution.Take by weighing the 76.662g Compound C
2With the 103.318g Compound D
7, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 60.0ml dehydrated alcohol again, stirred 1 hour.Then, at room temperature add compd B successively
2And compd A
3The carboxylate ethanolic soln, stirred under the room temperature 8 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 4 takes by weighing the 179.786g compd B
1, in the 660.9ml Virahol, reflux and obtain compd B
1Carboxylate solution; Take by weighing the 80.986g compd A
1, the backflow esterification obtains compd A in the 225.0ml Virahol
1Carboxylate solution.Take by weighing the 29.782g Compound C
1With the 109.743g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 200.0ml Virahol again, stirred 1.5 hours.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 7 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 5 takes by weighing the 211.652g compd B
1, the backflow esterification obtains compd B in the 557.1ml dehydrated alcohol
1Carboxylate solution; Take by weighing the 48.591g compd A
1, the backflow esterification obtains compd A in the 86.3ml dehydrated alcohol
1Carboxylate solution.Take by weighing the 29.929g Compound C
1With the 109.743g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 60.0ml dehydrated alcohol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 4 hours, obtain red homogeneous phase substrate resin solution.With this resin solution dipping chopped carbon fiber (T-300, length 10mm), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made molding after 50-350 ℃ of heat curing process moulding.The typical performance of this molding: flexural strength: 110MPa; Tensile strength: 80MPa; Unnotched impact strength: 20KJ/m
2
Embodiment 6. takes by weighing the 214.737g compd B
1, the backflow esterification obtains compd B in the 336.9ml anhydrous methanol
1Carboxylate solution; Take by weighing the 47.278g compd A
1, the backflow esterification obtains compd A in the 46.7ml anhydrous methanol
1Carboxylate solution.Take by weighing the 45.213g Compound C
1With the 82.879g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 70.0ml anhydrous methanol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 5 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 7. takes by weighing the 243.484g compd B
3, the backflow esterification obtains compd B in the 392.7ml anhydrous methanol
3Carboxylate solution; Take by weighing the 76.608g compd A
1, the backflow esterification obtains compd A in the 75.7ml anhydrous methanol
1Carboxylate solution.Take by weighing the 60.452g Compound C
1With the 30.225g Compound D
2, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 60.0ml dehydrated alcohol again, stirred 0.5 hour.Then, at room temperature add compd B successively
3And compd A
1Carboxylate solution, stirred under the room temperature 5 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 8. takes by weighing the 317.962g compd B
1, the backflow esterification obtains compd B in the 573.6ml dehydrated alcohol
1Carboxylate solution; Take by weighing the 45.959g compd A
1, the backflow esterification obtains compd A in the 81.6ml dehydrated alcohol
1Carboxylate solution.Take by weighing the 60.746g Compound C
1With the 55.688g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add dehydrated alcohol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 6 hours, obtain red homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 9. takes by weighing the 188.770g compd B
1, in the 296.1ml anhydrous methanol, reflux and obtain compd B
1Carboxylate solution; Take by weighing the 30.956g compd A
1, the backflow esterification obtains compd A in the 30.6ml anhydrous methanol
1Carboxylate solution.Take by weighing the 26.748g Compound C
1With the 98.084g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 120ml Virahol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 8 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 10. takes by weighing the 196.370g compd B
1, in the 721.9ml Virahol, reflux and obtain compd B
1Carboxylate solution; Take by weighing the 29.080g compd A
1, the backflow esterification obtains compd A in the 28.7ml anhydrous methanol
1Carboxylate solution.Take by weighing the 39.015g Compound C
1With the 71.533g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 100.0ml Virahol again, stirred 1 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 6 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Embodiment 11. takes by weighing the 197.925g compd B
1, in the 310.5ml anhydrous methanol, reflux and obtain compd B
1Carboxylate solution; Take by weighing the 28.142g compd A
1, the backflow esterification obtains compd A in the 50.0ml dehydrated alcohol
1Carboxylate solution.Take by weighing the 52.176g Compound C
1With the 47.831g Compound D
1, join N be housed
2In import and export and the churned mechanically three mouthfuls of reaction flasks, add the 110.0ml anhydrous isopropyl alcohol again, stirred 0.5 hour.Then, at room temperature add compd B successively
1And compd A
1Carboxylate solution, stirred under the room temperature 7 hours, obtain the homogeneous phase substrate resin solution.With this resin solution impregnation of carbon fibers (T-300), after handling, 40-220 ℃ of temperature programming make prepreg (band or cloth).This prepreg is made unidirectional laminate after 50-350 ℃ of heat curing process moulding.
Claims (4)
1. thermosetting polyimide base resin, in weight part, form by following component and content:
Reactive end-capping reagent 10-55
Aromatic series tetracarboxylic dianhydride 100
Aromatic diamine 35-110
Described reactive end-capping reagent means the organic compound with following chemical structure:
Described aromatic series tetracarboxylic dianhydride means organic compound and the isomer thereof with following chemical structure:
Described aromatic diamine is the mixture of aromatic diamine II or itself and aromatic diamine I;
Described aromatic diamine I means organic compound and the derivative thereof with following chemical structure:
Described aromatic diamine II means organic compound and the derivative thereof with following chemical structure:
2. the preparation method of a thermosetting polyimide base resin in weight part, follows these steps to carry out:
1. the reactive end-capping reagent of 10-55 part is refluxed in organic solvent and generate corresponding carboxylic acid monoesters solution (1);
2. 100 parts of aromatic series tetracarboxylic dianhydrides are refluxed in organic solvent and generate corresponding aroma family two acid diesters solution (2);
3. 35-110 part aromatic diamine is dissolved in the organic solvent, adds solution (1) and solution (2) then successively,, obtain substrate resin solution at 5-25 ℃ of following stirring reaction 1-7 hour;
4. substrate resin solution is adopted ordinary method to carry out thermofixation;
Described reactive end-capping reagent means the organic compound with following chemical structure:
Described aromatic series tetracarboxylic dianhydride means organic compound and the isomer thereof with following chemical structure:
Described aromatic diamine is the mixture of aromatic diamine II or itself and aromatic diamine I;
Described aromatic diamine I means organic compound and the derivative thereof with following chemical structure:
Described aromatic diamine II means organic compound and the derivative thereof with following chemical structure:
3. according to the preparation method of a kind of thermosetting polyimide base resin of claim 2, it is characterized in that: described organic solvent is ethanol, methyl alcohol, Virahol, propyl carbinol, N-Methyl pyrrolidone, N,N-dimethylacetamide or its mixture.
4. according to the preparation method of a kind of thermosetting polyimide base resin of claim 2, it is characterized in that: the consumption of the organic solvent of described reactions steps in 1. is 5-800 part (weight part); The consumption of the organic solvent of described reactions steps in 2. is 70-1400 part (weight part); The consumption of the organic solvent of described reactions steps in 3. is 5-3000 part (weight part).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118566 CN1123589C (en) | 2001-06-04 | 2001-06-04 | Thermosetting polyimide base resin and its prepn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01118566 CN1123589C (en) | 2001-06-04 | 2001-06-04 | Thermosetting polyimide base resin and its prepn. |
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| CN1389494A CN1389494A (en) | 2003-01-08 |
| CN1123589C true CN1123589C (en) | 2003-10-08 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7994274B2 (en) * | 2003-09-02 | 2011-08-09 | I.S.T. (Ma) Corporation | Two-stage cure polyimide oligomers |
| CN101698704B (en) * | 2006-11-17 | 2012-05-23 | 长兴化学工业股份有限公司 | Polyimide precursor composition and application thereof |
| CN101190969B (en) * | 2006-11-17 | 2010-05-19 | 长兴化学工业股份有限公司 | Precursor composition for polyimide and application thereof |
| CN101451013B (en) * | 2007-11-29 | 2011-05-25 | 比亚迪股份有限公司 | Polyimide material and preparation method thereof |
| CN101412812B (en) * | 2008-10-28 | 2011-07-20 | 上海三普化工有限公司 | Method for aqueous phase synthesis of polyimides |
| CN102120820B (en) * | 2011-01-26 | 2016-03-30 | 上海三普化工有限公司 | A kind of method of performing aqueous synthesis of thermosetting polyimide |
| CN103509186A (en) * | 2012-06-27 | 2014-01-15 | 比亚迪股份有限公司 | Polyamide acid solution and preparation method thereof, polyimide solution, polyimide porous membrane and lithium ion battery |
| CN102964834B (en) * | 2012-11-22 | 2015-03-11 | 中国科学院化学研究所 | High temperature-resistant anti-compression cross-linking polyimide foam material and preparation method and application thereof |
| CN105017769B (en) * | 2014-04-21 | 2018-08-14 | 中国科学院化学研究所 | Honeycomb thermosetting property rigid closed cell Polyimide foam composite material and the preparation method and application thereof |
| CN103980489B (en) * | 2014-04-30 | 2018-08-31 | 中国科学院化学研究所 | A kind of low melt viscosity thermoplastic polyimide material and its 3D printing forming method |
| CN106279688B (en) * | 2016-08-11 | 2019-01-11 | 中国科学院宁波材料技术与工程研究所 | Thermoset polyimide resin and its preparation method and application |
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