CN1176975C - Preparation of polyimide moulded by casting - Google Patents
Preparation of polyimide moulded by castingInfo
- Publication number
- CN1176975C CN1176975C CNB021589240A CN02158924A CN1176975C CN 1176975 C CN1176975 C CN 1176975C CN B021589240 A CNB021589240 A CN B021589240A CN 02158924 A CN02158924 A CN 02158924A CN 1176975 C CN1176975 C CN 1176975C
- Authority
- CN
- China
- Prior art keywords
- diamino
- bismaleimides
- oligopolymer
- diaminodiphenyl
- casting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Abstract
The present invention belongs to a preparation method of casting mouldable polyimide. A crosslinkable active solvent and a bismaleimide oligomer are adopted to form a solution or pulp, a casting mouldable prepolymer material is formed and polymerized at the room temperature through irradiation or polymerized at the initiation temperature of an initiating agent, the irradiation dose is from 10 to 200 Kgy, and the initiating agent is azodiisobutyronitrile or dibenzoyl peroxide. Various complicated polyimide prepared pieces can be prepared by utilizing the characteristic of low viscosity of a prepolymer solution to effectively reduce the cost for the processing of the polyimide and reduce the technology difficulty.
Description
Technical field
The invention belongs to preparation of polyimide moulded by casting.
Background technology
Polyimide is used widely on Aeronautics and Astronautics, various electric insulation, machinery, separatory membrane and microelectronics industry as the resistant to elevated temperatures polymer materials of a class.But this class material is normally processed by solution or toner fusion, thereby makes various products.As having reported in the United States Patent (USP)s in 2000 6,025,460 in the polar solvent N-Methyl pyrrolidone by the fibre-reinforced composite material presoaked liquid of pyrocondensation prepared in reaction.Reported the polyimide fiber for preparing high-strength and high-modulus by polyamic acid solution in the United States Patent (USP) 4,640,972 in 1987.Help the volatilization of solvent the solution from formulations prepared from solutions thin layer product and obtain the product of excellent performance.United States Patent (USP) 6 in 2000,036,900 and 5,493,002 has reported the preparation of thermoset polyimide resin respectively, all owing to the higher softening temperature of polyimide resin and higher melt viscosity and need its fusion just can be obtained required goods in conditions such as High Temperature High Pressure.Though these methods also can make the material of excellent performance, make that all its complete processing is complicated, also cause the rising of cost simultaneously, and can only prepare comparatively simple product for various reasons mostly, be difficult to prepare the comparatively complicated product of structure.And yet there are no report about the polyimide simple and convenient process for preparing that at room temperature directly carries out casting forming.
Summary of the invention
The purpose of this invention is to provide a kind of preparation of polyimide moulded by casting.
The present invention adopts crosslinkable strong solvent and bismaleimide amine oligomer to form solution or soup compound, constitute the pre-polymerization material of moulded by casting, utilize the pre-polymer solution low viscosity characteristics, moulding at a lower temperature, can carry out the preparation of various complicated polyimide products, after this system is cast in mould, can be at room temperature with irradiation or polymerization under the initiator kick off temperature, obtain required goods, effectively reduced the difficulty of polyimide cost of processing and technology.
Strong solvent of the present invention is: N, N`-DMAA, acrylamide, N-vinyl-2-is than pyrrolidone, 2-vinyl pyridine, 4-vinylpridine, wherein one or more of vinylbenzene, Vinylstyrene, methyl methacrylate or third rare cyanogen;
Bismaleimide amine oligomer of the present invention has following general structure:
N 〉=0 wherein;
Oligopolymer is that bismaleimides and diamine form through polycondensation, and the diamine that is comprised in the bismaleimide amine oligomer has:
Ursol D, mphenylenediamine, 4, the 4`-diaminodiphenyl oxide, 3, the 4`-diaminodiphenyl oxide, 4, the 4`-diaminodiphenyl-methane, 3,3`-dimethyl-4, the 4`-diaminodiphenyl-methane, 3,3`-two chloro-4, the 4`-diaminodiphenyl-methane, 2, the 2`-tolidine, 3, the 3`-tolidine, 4,4`-diamino-sulfobenzide, 4,4`-diamino-hexichol Oxy-1 ``, 4``-benzene, 4,4`-diamino-hexichol Oxy-1 ``, 3``-benzene, 3,3`-diamino-hexichol Oxy-1 ``, 3``-benzene, 4,4`-diamino-two phenoxy groups-4``, the different propane of 4```-phenylbenzene or 4,4`-diamino-two phenoxy groups-4``, the 4```-sulfobenzide.
The oligopolymer blend of strong solvent and bismaleimides is formed solution or soup compound, and the mass content of the oligopolymer of bismaleimides is the 5%-80% of solution or soup compound; Adopt
60Co radiation, dosage are 10-200KGy; Active solidified initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide; The consumption of initiator is the 0.1%-0.5% of solution or soup compound quality; The casting matrix after fixing temperature of preparation is 120-220 ℃; Set time 2-20h.
Embodiment
Embodiment 1:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 50KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.5% thermal weight loss is 340 ℃, and bending strength is 151MPa, and composite bending modulus is 3.05GPa, and ultimate compression strength is 129MPa, and compression modulus is 1.49MPa, and shock strength is 35KJ/m
2, saturated water absorption is 7%.
Embodiment 2:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 4: 3 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.5% thermal weight loss is 362 ℃, and bending strength is 114MPa, and composite bending modulus is 2.86GPa, and ultimate compression strength is 116MPa, and compression modulus is 0.98MPa, and shock strength is 24KJ/m
2, saturated water absorption is 10%.
Embodiment 3:
With 12g 3,3`-dimethyl-4,4`-diaminodiphenyl-methane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 2: 1 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 4:
With 10g 4,4`-diamino-two phenoxy groups-4``, different propane of 4```-phenylbenzene and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10gN, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 180 ℃ of after fixing 4h, obtain amber clear sheet after the demoulding.
Embodiment 5:
With 10g 4,4`-diaminodiphenyl oxide and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 6: 5 (mol ratio) prepared oligopolymer and 7g N, after N`-DMAA, 3g acrylamide mix stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 200KGy, at 180 ℃ of after fixing 10h, obtain amber clear sheet after the demoulding.
Embodiment 6:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 12g N, after N`-DMAA and 3g methyl methacrylate mix stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 50KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 7:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, after N`-DMAA and 3g third rare cyanogen mix stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 50KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 8:
With 10g 3,4`-diaminodiphenyl oxide and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 5g N, after N`-DMAA and 5g4-vinyl pyridine mix stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 9:
With 10g mphenylenediamine and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 8g N, after N`-DMAA and 2g Vinylstyrene mix stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 10:
With 10g 4,4`-diamino-sulfobenzide and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 11:
With 10g 4,4`-diamino-hexichol Oxy-1 ``, 4``-benzene and N, N`-bismaleimides-4, the 4`-ditan with the prepared oligopolymer of the ratio of 3: 2 (mol ratio) with after 10g N-vinyl-2-Pyrrolidone mixes stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 180 ℃ of after fixing 16h, obtain amber clear sheet after the demoulding.
Embodiment 12:
With 10g 4,4`-diamino-hexichol Oxy-1 ``, 3``-benzene and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 4h, obtain amber clear sheet after the demoulding.
Embodiment 13:
With 10g 3,3`-diamino-hexichol Oxy-1 ``, 3``-benzene and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 50KGy, at 180 ℃ of after fixing 2h, obtain amber clear sheet after the demoulding.
Embodiment 14:
With 10g 4,4`-diamino-two phenoxy groups-4``, different propane of 4```-phenylbenzene and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10gN, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 20KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 15:
With 10g 4,4`-diamino-two phenoxy groups-4``, 4```-sulfobenzide and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 20KGy, at 180 ℃ of after fixing 3h, obtain amber clear sheet after the demoulding.
Embodiment 16:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, after the 4`-ditan mixes stirring and dissolving with the prepared oligopolymer of the ratio of 3: 2 (mol ratio) and 6g N-vinyl-2-than pyrrolidone and 4g 2-vinyl pyridine, the decompression degassing, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 150KGy, at 220 ℃ of after fixing 6h, get amber clear sheet after the demoulding.
Embodiment 17:
With 10g 4,4`-diamino-two phenoxy groups-4``, different propane of 4```-phenylbenzene and N, N`-bismaleimides-4, the 4`-ditan with the prepared oligopolymer of the ratio of 3: 2 (mol ratio) with after 10gN-vinyl-2-Pyrrolidone mixes stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 18:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan with the prepared oligopolymer of the ratio of 3: 2 (mol ratio) with after 7g N-vinyl-2-Pyrrolidone and 3g vinylbenzene mix stirring and dissolving, the decompression degassing, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 150 ℃ of after fixing 12h, obtain amber clear sheet after the demoulding.
Embodiment 19:
With 10g 4,4`-diamino-hexichol Oxy-1 ``, 3``-benzene and N, N`-bismaleimides-4, the 4`-ditan with the prepared oligopolymer of the ratio of 3: 2 (mol ratio) with after 10g N-vinyl-2-Pyrrolidone mixes stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 20:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 5: 4 (mol ratio) prepared oligopolymer and 10g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 21:
With 10g 4,4`-diamino-hexichol Oxy-1 ``, 3``-benzene and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 20g N, and after the N`-DMAA mixed stirring and dissolving, decompression outgased, pour in the mould of making by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 120KGy, at 200 ℃ of after fixing 15h, obtain amber clear sheet after the demoulding.
Embodiment 22:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4,4`-ditan are with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 5g N, after N`-DMAA and 5g N-vinyl-2-Pyrrolidone mixes stirring and dissolving, add the 0.03g dibenzoyl peroxide, the decompression degassing is poured in the mould, places 12h at 80 ℃, at 150 ℃ of after fixing 20h, the demoulding obtains amber clear sheet again.
Embodiment 23:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4,4`-ditan are with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 5g N, after the N`-DMAA mixes stirring and dissolving, add the 0.03g Diisopropyl azodicarboxylate, the decompression degassing is poured in the mould, places 24h at 80 ℃, at 160 ℃ of after fixing 12h, the demoulding obtains amber clear sheet again.
Embodiment 24:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 5g vinylbenzene and 10g N, after the N`-DMAA mixes stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 180 ℃ of after fixing 6h, obtain amber clear sheet after the demoulding.
Embodiment 25:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the ratio of 3: 2 (mol ratio) prepared oligopolymer and 5g methyl methacrylate and 10gN, after the N`-DMAA mixes stirring and dissolving, the decompression degassing is poured in the mould of being made by sheet glass,
60Be irradiated to dosage under the room temperature in the Co source and reach 100KGy, at 120 ℃ of after fixing 20h, obtain amber clear sheet after the demoulding.
Embodiment 26:
With 10g 4,4`-diaminodiphenylmethane and N, N`-bismaleimides-4, the 4`-ditan is with the prepared oligopolymer of the ratio of 3: 2 (mol ratio), 7g vinylbenzene and 8g N, after the N`-DMAA mixes stirring and dissolving, the decompression degassing adds the 0.05g dibenzoyl peroxide, the decompression degassing, pour in the mould, place 20h at 80 ℃, at 160 ℃ of after fixing 10h, obtain amber clear sheet after the demoulding.
Claims (1)
1. preparation of polyimide moulded by casting, it is characterized in that the strong solvent that adopts is: N, the N`-DMAA, acrylamide, N-vinyl-2-Pyrrolidone, 2-vinyl pyridine, 4-vinylpridine, wherein one or more of vinylbenzene, Vinylstyrene, methyl methacrylate or propylene cyanogen;
The bismaleimide amine oligomer that adopts has following general structure:
N 〉=0 wherein, H
2N-Ar-NH
2Be Ursol D, mphenylenediamine, 4, the 4`-diaminodiphenyl oxide, 3, the 4`-diaminodiphenyl oxide, 4, the 4`-diaminodiphenyl-methane, 3,3`-dimethyl-4, the 4`-diaminodiphenyl-methane, 3,3`-two chloro-4, the 4`-diaminodiphenyl-methane, 2, the 2`-tolidine, 3, the 3`-tolidine, 4,4`-diamino-sulfobenzide, 4,4`-diamino-hexichol Oxy-1 ``, 4``-benzene, 4,4`-diamino-hexichol Oxy-1 ``, 3``-benzene, 3,3`-diamino-hexichol Oxy-1 ``, 3``-benzene, 4,4`-diamino-two phenoxy groups-4``, the different propane of 4```-phenylbenzene or 4,4`-diamino-two phenoxy groups-4``, the 4```-sulfobenzide;
Oligopolymer is that bismaleimides and diamine form through polycondensation;
The oligopolymer blend of strong solvent and bismaleimides is formed solution or soup compound, and the mass content of the oligopolymer of bismaleimides is the 5%-80% of solution or soup compound; Adopt
60Co radiation, dosage are 10-200KGy; Active solidified initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide; The consumption of initiator is the 0.1%-0.5% of solution or soup compound quality; The casting matrix after fixing temperature of preparation is 120-220 ℃; Set time 2-20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021589240A CN1176975C (en) | 2002-12-27 | 2002-12-27 | Preparation of polyimide moulded by casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021589240A CN1176975C (en) | 2002-12-27 | 2002-12-27 | Preparation of polyimide moulded by casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424340A CN1424340A (en) | 2003-06-18 |
| CN1176975C true CN1176975C (en) | 2004-11-24 |
Family
ID=4753208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021589240A Expired - Fee Related CN1176975C (en) | 2002-12-27 | 2002-12-27 | Preparation of polyimide moulded by casting |
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| CN (1) | CN1176975C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139416B (en) * | 2006-09-05 | 2010-07-28 | 中国石油天然气股份有限公司 | Method for preparing maleimide heat-proof resin emulsion |
| CN102580580B (en) * | 2012-02-27 | 2014-05-28 | 北京市射线应用研究中心 | Polyimide gas separation membrane and preparation method thereof |
| CN102660024B (en) * | 2012-05-24 | 2013-10-16 | 黑龙江大学 | Electrochromatic bismaleimide resin and preparation method of film of electrochromatic bismaleimide resin |
| CN103208604B (en) * | 2013-03-18 | 2015-06-03 | 厦门大学 | Electrospinning composite diaphragm with thermal hole sealing function |
| CN108099340B (en) * | 2016-08-31 | 2019-09-24 | 苏州凯英工业材料有限公司 | A kind of composite polyimide material |
| CN106496558B (en) * | 2016-11-04 | 2019-03-08 | 沈阳航空航天大学 | One kind can response type poly (arylene ether nitrile) imide resin and preparation method thereof |
| WO2018107453A1 (en) * | 2016-12-16 | 2018-06-21 | 株式会社大赛璐 | Curing compound |
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2002
- 2002-12-27 CN CNB021589240A patent/CN1176975C/en not_active Expired - Fee Related
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| CN1424340A (en) | 2003-06-18 |
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