CN100482718C - Polyimide semi-interpenetrating network resin and its prepn. method - Google Patents
Polyimide semi-interpenetrating network resin and its prepn. method Download PDFInfo
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- CN100482718C CN100482718C CNB2006100165692A CN200610016569A CN100482718C CN 100482718 C CN100482718 C CN 100482718C CN B2006100165692 A CNB2006100165692 A CN B2006100165692A CN 200610016569 A CN200610016569 A CN 200610016569A CN 100482718 C CN100482718 C CN 100482718C
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Abstract
The invention belongs to the domain of the polymers technology and is the polyimide half interpenetrating networks pitch and the producing process. With the method of the dry mixing, the wet mixing or the melt mixing, the tri-benzene bis ether polyimide with thermal plasticity is combined with the thermoset bi-smaleimide, then the half interpenetrating networks is formed by the hot pressing. The dosage of the tri-benzene bis ether polyimide is 5-90 percentage and 10-70 percentage optimally. The mixed pitch can be shared with other filler material such as the fraphite, the supramoly, the silicon dioxide, the titanium dioxide, the polyetrafluoroethylene, the carbon fiber and the fibergals in order to improve the ability of the engineering plastic and to satisfy the consumer. Using the high tenacity of the tri-benzene bis ether polyimide with thermal plasticity to reinforce the rigid cross linked structure of the bismaleimide, we can gain the half interpenetrating of the high tenacity and the intension; the material requirement of the different capability needed by a vatiety of purpose can be satisfied by the different mixing methods.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of engineering plastics, specifically a kind of polyimide semi-intercrossing network resin and preparation method thereof.
Background technology
Polyimide is the highest engineering plastics of present use temperature, can be divided into thermoset and thermoplasticity two classes.Thermoplastic polyimide is processed easily, and over-all properties is outstanding; Thermocurable polyimide use temperature height, but more crisp.Thermoplastic polyimide and Thermocurable polyimide are combined, can bring out one's strengths to make up for one's weaknesses, obtain the comprehensive engineering plastics of performance.
Summary of the invention
The present invention is to be raw material with thermoplasticity triphen diether type polyimide and thermoset bismaleimides, mixes by doing, wet mixing or melting mixing make its combination, and purpose provides a kind of polyimide semi-intercrossing network resin and preparation method thereof.
The used raw material of the present invention is thermoplasticity triphen diether type polyimide and thermoset bismaleimides.Wherein the content of triphen diether type polyimide is 5-90% by weight percentage, and the best is 10-70%.Make thermoplasticity triphen diether type polyimide and the combination of thermoset bismaleimides with blending means, formation can obtain the resin of half interpenetrating network structure.Described half interpenetrating network structure is to intert the linear macromolecule of thermal plastic high polymer in the network that thermosetting resin is cross-linked to form, and forming an existing resistant to elevated temperatures cross-linked network has the flexible of increasing long-chain system again.
Described preparation method have do to mix, wet mixing and melting mixing.Mix the resin that the back forms semi-intercrossing network, can also add other packing materials simultaneously,,, reach user's various requirement to improve the performance of engineering plastics as graphite, molybdenumdisulphide, tetrafluoroethylene, carbon fiber, glass fibre etc.
The structure of described triphen diether type thermoplastic polyimide is:
Wherein Ar is following group:
The structure of described thermoset bismaleimides is:
The used preparation method of the present invention has:
1. do and mix.Described dried mixing is that a certain proportion of triphen diether type thermoplastic polyimide (thermoplastic polyimide) powder and bismaleimides powder are used behind the mixing in homogenizer.
2. wet mixing.Described wet mixing is with a certain proportion of triphen diether type thermoplastic polyimide (thermoplastic polyimide) resin and bismaleimides powder 100-140 ℃ of mixing and stirring in phenol solvent, precipitates in ethanol then, and use the dry back of washing.
3. melting mixing.Described melting mixing is that the bismaleimides powder is added a certain proportion of triphen diether type thermoplastic polyimide (thermoplastic polyimide) powder after 150 ℃ of fusions, and the mixing postcooling is pulverized the back and used.
The semi-intercrossing network resin that is obtained by method recited above can also add weight percent in preparation process be 1-70% other inorganic fillings, come modification as graphite, charcoal fiber, glass fibre, silicon-dioxide, titanium dioxide, molybdenumdisulphide and polytetrafluorethylepowder powder, to obtain to be used for the PP Pipe Compound of various purposes.These PP Pipe Compound can be at 360-380 ℃, and compression molding under 10MPa or the higher pressure obtains various goods.
The present invention utilizes the high tenacity of triphen diether type thermoplastic polyimide and intensity to strengthen bismaleimides inflexible crosslinking structure, both had high heat resistance, the semi-intercrossing network polyimide resin that has high tenacity and intensity again obtains satisfying the requirement of various uses to the different performance of material with different blending meanss.With simple ratio of component, the cross-linked polymer of bismaleimides is too crisp, can't use, tend to reduce use temperature or only have lower mechanical property, so the more uses of the resin of Bismaleimide Resin are on fibre composite with other component copolymerization.Use semi-intercrossing network resin of the present invention, enhancement by thermoplastic polyimide, the plastics that both can obtain virgin resin also can add the engineering plastics that other additives obtain having higher mechanical property or frictional behaviour, so have wide application field.
Embodiment
In order more to be expressly understood the present invention, below provide embodiments of the invention.
Embodiment 1
70g thermoplastic polyimide powder is mixed 2min with 30g bismaleimides powder and 10g graphite in homogenizer, the mould mold pressing under 380 ℃ of 20Mpa of packing into of the resulting compound (hereinafter to be referred as compound) that can form semi-intercrossing network is obtained the sheet material that thickness is 5mm.
Embodiment 2
The solution of 70g thermoplastic polyimide in 600ml cresols is mixed 30min with 30g bismaleimides powder and 10g carbon fiber at 120 ℃, pour in the 2000ml ethanol, with cold washing with alcohol 3 times, 70 ℃ of vacuum-dryings obtain compound with the precipitation that obtains.
Embodiment 3
With the fusion in 150 ℃ of thermostatic baths of 30g bismaleimides, stir adding 30g thermoplastic polyimide and 5g polytetrafluorethylepowder powder down, restir 2min, cooling is pulverized, and obtains compound.
Embodiment 4
90g thermoplastic polyimide powder, 10g bismaleimides powder, 5g graphite, 5g tetrafluoroethylene and 10g carbon fiber are mixed 2min in high-speed mixer, obtain compound.
Embodiment 5
90g thermoplastic polyimide powder, 10g bismaleimides powder, 5g graphite, 3g molybdenumdisulphide and 5g glass fibre are mixed 2min in the high speed blender, obtain compound.
Embodiment 6
70g thermoplastic polyimide powder and 30g bismaleimides powder and 50g glass fibre, 10g graphite are mixed 5min in the high speed blender, obtain compound.
Embodiment 7
The solution of 60g thermoplastic polyimide in 600ml cresols is mixed 30min with 40g bismaleimides powder and 5g molybdenumdisulphide, 5g tetrafluoroethylene and 10g carbon fiber at 120 ℃, pour in the 2000ml ethanol, with cold washing with alcohol 3 times, 70 ℃ of vacuum-dryings obtain compound with the precipitation that obtains.
Embodiment 8
With the fusion in 150 ℃ of thermostatic baths of 50g bismaleimides, stir adding 30g thermoplastic polyimide and 5g polytetrafluorethylepowder powder and 5g graphite down, restir 2min, cooling is pulverized, and obtains compound.
Embodiment 9
50g thermoplastic polyimide powder and 50g bismaleimides powder and 30g glass fibre, 10g titanium dioxide are mixed 5min in the high speed blender, obtain compound.
Embodiment 10
50g thermoplastic polyimide powder and 50g bismaleimides powder and 30g silicon-dioxide, 10g graphite are mixed 5min in the high speed blender, obtain compound.
Claims (8)
1, a kind of polyimide semi-intercrossing network resin, it is characterized in that with triphen diether type thermoplastic polyimide and thermoset bismaleimides mix by doing, wet mixing or melting method make its mixing, obtaining interting in the network that thermosetting resin is cross-linked to form the half interpenetrating network structure of linear macromolecule of thermal plastic high polymer after the hot-work, wherein the content of triphen diether type polyimide is 5-90% by weight percentage;
The structure of described triphen diether type thermoplastic polyimide is:
Wherein Ar is following group:
The structure of described thermoset bismaleimides is:
2, polyimide semi-intercrossing network resin according to claim 1 is characterized in that being filled with graphite, molybdenumdisulphide, tetrafluoroethylene, carbon fiber or glass fibre at half interpenetrating network structure.
3, polyimide semi-intercrossing network resin according to claim 1 and 2, the content that it is characterized in that triphen diether type polyimide is 10-70% by weight percentage.
4, the preparation method of polyimide semi-intercrossing network resin according to claim 1, it is characterized in that used preparation method mixes for doing, described dried mixing is that a certain proportion of triphen diether type thermoplastic polyimide powder and bismaleimides powder are used behind the mixing in the high-ductility stirrer.
5, the preparation method of polyimide semi-intercrossing network resin according to claim 1, it is characterized in that used preparation method is wet mixing, described wet mixing be with a certain proportion of triphen diether type thermoplastic polyimide resin and bismaleimides powder in phenol solvent, in 100-140 ℃ of mixing and stirring of temperature, precipitate in ethanol then, use the dry back of washing.
6, the preparation method of polyimide semi-intercrossing network resin according to claim 1, it is characterized in that used preparation method is a melting mixing, described melting mixing is that the bismaleimides powder is added a certain proportion of triphen diether type thermoplastic polyimide powder after 150 ℃ of fusions, the mixing postcooling is pulverized the back and is used.
7, polyimide semi-intercrossing network process for preparing resins according to claim 4, add graphite, molybdenumdisulphide, tetrafluoroethylene, carbon fiber or glass fibre packing material in the resin of the formation semi-intercrossing network that obtains after it is characterized in that mixing, it is filled in the half interpenetrating network structure at last.
8, polyimide semi-intercrossing network process for preparing resins according to claim 5 is characterized in that the amount weight percent of the packing material that adds is 1-70%.
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| CNB2006100165692A CN100482718C (en) | 2006-01-26 | 2006-01-26 | Polyimide semi-interpenetrating network resin and its prepn. method |
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| CNB2006100165692A CN100482718C (en) | 2006-01-26 | 2006-01-26 | Polyimide semi-interpenetrating network resin and its prepn. method |
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| CN100482718C true CN100482718C (en) | 2009-04-29 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788953A (en) * | 2015-04-17 | 2015-07-22 | 广西藤县通轩立信化学有限公司 | Polyimide resin composition |
| CN106674874A (en) * | 2016-12-29 | 2017-05-17 | 江阴标榜汽车部件有限公司 | High-strength multifunctional composite electric control tube for sedan and preparation method of electric control tube |
| CN107057267A (en) * | 2016-12-29 | 2017-08-18 | 江阴标榜汽车部件有限公司 | Car high-low temperature resistant antiseep breather pipe and preparation method thereof |
| CN106674873A (en) * | 2016-12-29 | 2017-05-17 | 江阴标榜汽车部件有限公司 | High-strength high temperature-resisting cooling water pipe for saloon car and preparation method thereof |
| CN106905914B (en) * | 2017-03-01 | 2019-09-24 | 成都正威新材料研发有限公司 | A kind of semi-intercrossing network polyimide resin composition and its membranaceous adhesive of preparation |
| CN108752928B (en) * | 2018-05-03 | 2021-03-09 | 中国科学院宁波材料技术与工程研究所 | Cross-linked polyimide resin containing furan ring and preparation method thereof |
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|---|---|---|---|---|
| US4714642A (en) * | 1983-08-30 | 1987-12-22 | Basf Aktiengesellschaft | Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation |
| US4956393A (en) * | 1988-08-29 | 1990-09-11 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| CN1080643A (en) * | 1992-06-22 | 1994-01-12 | 蓬莱市大雪实业总公司 | Double maleie polyimide modified resin and manufacture method |
| CN1156733A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Dimaleic type liquid crystal polyimide and its preparing process |
| CN1098879C (en) * | 2000-03-14 | 2003-01-15 | 复旦大学 | Polyetherimide modified bimalieimide resin |
-
2006
- 2006-01-26 CN CNB2006100165692A patent/CN100482718C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714642A (en) * | 1983-08-30 | 1987-12-22 | Basf Aktiengesellschaft | Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation |
| US4956393A (en) * | 1988-08-29 | 1990-09-11 | Basf Aktiengesellschaft | Structures exhibiting improved transmission of ultrahigh frequency electromagnetic radiation and structural materials which allow their construction |
| CN1080643A (en) * | 1992-06-22 | 1994-01-12 | 蓬莱市大雪实业总公司 | Double maleie polyimide modified resin and manufacture method |
| CN1156733A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Dimaleic type liquid crystal polyimide and its preparing process |
| CN1098879C (en) * | 2000-03-14 | 2003-01-15 | 复旦大学 | Polyetherimide modified bimalieimide resin |
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Owner name: CHANGCHUN GAOQI POLYIMIDE MATERIAL CO., LTD. Free format text: FORMER NAME: SPECIAL ENGINEERING PLASTICS CO., LTD., OF CHANGCHUN APPLIED CHEMICAL CORP. |
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Address after: 130103, 666B, super street, hi tech Zone, Jilin, Changchun Patentee after: Changchun Hipolyking Co., Ltd. Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Special Engineering Plastics Co., Ltd., of Changchun Applied Chemical Corp. |