CN104761915A - Preparation method of wear-resistant polyimide and fluorine-containing polymer composition - Google Patents
Preparation method of wear-resistant polyimide and fluorine-containing polymer composition Download PDFInfo
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Abstract
The invention discloses a preparation method of wear-resistant polyimide and fluorine-containing polymer composition, which comprises the following steps: a)mixing the following components by weight part: 90-98.9 parts of fluorine-containing polymer micro powder, 1-5 parts of metal hydroxides and 0.1-5 parts of processing auxiliary agent for 0.5-1 hour at temperature of 15-25 DEG C under 100-300rpm to obtain a fluorine-containing polymer micro powder premix; and b)mixing the following components by weight part: 80-98 parts of polyimides powder and 2-20 parts of the fluorine-containing polymer micro powder premix for 0.5-1 hour at temperature of 15-25 DEG C under 100-300rpm, extruding through a double screw extruder, and granulating and shaping to obtain the wear-resistant polyimide and fluorine-containing polymer composition. According to the invention, the process is simple, industrialization is easy, the friction coefficient and friction loss rate of the obtained wear-resistant polyimide and fluorine-containing polymer composition are low, and the composition can be used for fields of military, aviation spaceflight, precision machinery, machinery, electron, automobile, food and medical treatment.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to the preparation method of a kind of wear-resisting polyimide and fluoro-containing copolymer composition.
Background technology
Polyimide is as the one of special engineering plastics, because it has excellent high temperature resistant, low temperature resistant, high-strength and high-modulus, high creep resistance, high dimensional stabilizing, low thermal coefficient of expansion, high electric insulation, low-k and loss, radiation hardness, the advantage such as corrosion-resistant, be widely used in microelectronics industry and aerospace material.Fluoropolymer particularly ptfe micropowder has the performances such as high thermal stability, chemical resistance and self-lubricating, add in polyimide material, prepare wear-resisting ptfe micropowder/polyimide intermingling material, be widely used in the parts such as the sliding surface bearing in the fields such as aerospace, automobile, machinery, electronic apparatus, thrust washer, sealing-ring, blade, valve seat, axle bush and wear-resistant pad.
External ptfe micropowder/polyimide intermingling material has GE company Ultem series, the Aurum series of Mitsui company, the Torlon series of Solvay company, the Vespel series of Dupont company and the Tecasint series etc. of Ensinger company.Domestic Chinese Academy of Sciences orchidization study and Nanjing University of Technology also have correlative study to report.At present, preparing ptfe micropowder/polyimide intermingling material traditional method is both at home and abroad directly the method that ptfe micropowder mixes with polyimide obtained composition or adopt tensio-active agent by after ptfe micropowder surface treatment, mix with polyimide, obtained composition, makes parts after processing.This method is intended to the surface polarity changing ptfe micropowder, increases the physical compatibility with polyimide, improves the dispersiveness of ptfe micropowder in matrix resin polyimide, and then evenly increases the wear resistance of polyimide intermingling material.But, in the intermingling material prepared by above-mentioned traditional method, be Physical interaction between ptfe micropowder and polyimide molecule, in use, the easy loss of ptfe micropowder, intermingling material crocking resistance reduces gradually, and the work-ing life of intermingling material is low.
For overcome above-mentioned intermingling material in use crocking resistance reduce gradually, cause the problem that intermingling material work-ing life is low, be now badly in need of the preparation method exploring the stable ptfe micropowder/polyimide compositions of a kind of crocking resistance.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, there is provided simple, the easy industrialization of a kind of technique, obtained composition frictional coefficient and frictional dissipation rate low, the wear-resisting polyimide of long product lifecycle and the preparation method of fluoro-containing copolymer composition after forming process.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: the preparation method of a kind of wear-resisting polyimide and fluoro-containing copolymer composition, comprises the following steps:
(a) by weight, by fluoropolymer micro mist 90 ~ 98.9 parts, metal hydroxides 1 ~ 5 part, processing aid 0.1 ~ 5 part, at 15 ~ 25 DEG C, under 100 ~ 300rpm mix 0.5 ~ 1h, obtain the Preblend of fluoropolymer micro mist;
B () by weight, by polyimide powder 80 ~ 98 parts, the fluoropolymer micro mist Preblend 2 ~ 20 parts that step (a) obtains, at 15 ~ 25 DEG C, after mixing 0.5 ~ 1h under 100 ~ 300rpm, extrude through twin screw extruder, granulating and forming, obtain wear-resisting polyimide and fluoro-containing copolymer composition.
Described fluoropolymer micro mist is preferably the one in proplast micro mist, tetrafluoroethylene and chlorotrifluoroethylene micro mist, tetrafluoroethylene and vinylidene fluoride copolymers micro mist, tetrafluoroethylene and hexafluoropropylene copolymer micro mist, tetrafluoroethylene and perfluoro propyl vinyl ether copolymer micropowders, tetrafluoroethylene and perfluoroethylvinyl ether copolymer micropowders, tetrafluoroethylene and perfluoro methyl vinyl ether copolymer micropowders.
Described fluoropolymer micro mist median size is preferably 500nm ~ 15 μm, is more preferably 2 ~ 8 μm.
Described metal hydroxides is preferably Ca (OH)
2, Mg (OH)
2, Zn (OH)
2, Cu (OH)
2, Al (OH)
3in one or both mixture.
Described processing aid is preferably the one in methyl methacrylate/acrylic acid ester copolymer, methyl methacrylate/styrol copolymer, vinyl cyanide/styrol copolymer.
The mixing section temperature of described twin screw extruder is preferably 250 ~ 280 DEG C, and hot melt section temperature is preferably 330 ~ 350 DEG C, and compression section temperature is preferably 310 ~ 330 DEG C, and die head temperature is preferably 300 ~ 320 DEG C.
The present invention by the surface treatment of fluoropolymer micro mist and pre-mixing, to extrude with polyimide mix, the technique of obtained composition, polyimide and fluoropolymer micro mist molecule are carried out chemical bond-linking and obtain composition.Solve in composition prepared by traditional method and be only Physical interaction between fluoropolymer micro mist and polyimide molecule, in use, the easy loss of fluoropolymer micro mist, composition crocking resistance reduces gradually, causes the problem that composition work-ing life is low.This preparation method technique is simple, easily realizes industrialization, obtained composition frictional coefficient and frictional dissipation rate low, composition can be applicable to the fields such as military affairs, aerospace, precision optical machinery, machinery, electronics, automobile, food medical treatment by forming process.
At present, fluoropolymer micro mist generally adopts cracking process or direct polymerization method to prepare, and the fluoropolymer micro mist in the present invention can adopt a kind of obtained copolymer micropowders in proplast micro mist or tetrafluoroethylene and trifluorochloroethylene, vinylidene, R 1216, perfluoro propyl vinyl ether, perfluoroethylvinyl ether, perfluoro methyl vinyl ether.By direct polymerization legal system in ptfe micropowder process, the kind of initiator and telogen determines the unit structure of ptfe micropowder end group, by using different initiators and telogen, the end moieties of ptfe micropowder can be carboxylic acid, hydroxyl, sulfonic acid or sulfate group, these groups can with open loop after the imine group that formed of polyimide and hydroxy-acid group react under certain condition, polyimide and the intermolecular generation chemical bond-linking of ptfe micropowder, reduce frictional coefficient and the frictional dissipation of composition, extend the work-ing life of the rear product of composition molding processing.Therefore, fluoropolymer micro mist of the present invention is preferably the one in proplast micro mist, tetrafluoroethylene and chlorotrifluoroethylene micro mist, tetrafluoroethylene and vinylidene fluoride copolymers micro mist, tetrafluoroethylene and hexafluoropropylene copolymer micro mist, tetrafluoroethylene and perfluoro propyl vinyl ether copolymer micropowders, tetrafluoroethylene and perfluoroethylvinyl ether copolymer micropowders, tetrafluoroethylene and perfluoro methyl vinyl ether copolymer micropowders.
The dispersiveness of " sea-island " structure that the median size of fluoropolymer micro mist is formed when being mixed into polyimide to it has direct relation, the dispersiveness of fluoropolymer micro mist directly has influence on the performance of product after fluoropolymer micro mist and polyimide blend composition and forming process thereof, therefore, the median size of fluoropolymer micro mist of the present invention is preferably 500nm ~ 15 μm, is more preferably 2 ~ 8 μm.
Polyimide is under water, acid/alkali existence and certain temperature, imide group generation open loop, form imine group or hydroxy-acid group, metal hydroxides can resolve into the metal hydroxides of metal oxide and water molecules in a heated condition, like this, can be scattered in composition uniformly on the one hand, imide open loop be distributed in the composition relatively uniform, the probability that the group formed after improving imide group open loop and fluoropolymer end group react; Form inorganic oxide on the other hand, increase wear resistance and the mechanical property of composition, make up the impact added intermingling material mechanical property of fluoropolymer micro mist.Metal hydroxides of the present invention is Ca (OH)
2, Mg (OH)
2, Zn (OH)
2, Cu (OH)
2, Al (OH)
3in one or both mixture.
After polyimide mixes with the Preblend of fluoropolymer micro mist, need to make polyimide melting under certain condition, simultaneously polyimide and fluoropolymer react and need certain temperature equally, react temperature required according to the rheological property of polyimide and polyimide open loop and fluoropolymer, therefore the present invention extrudes through twin screw extruder, granulator granulation is shaping, obtain wear-resisting polyimide and ptfe micropowder composition, the mixing section temperature of twin screw extruder is preferably 250 ~ 280 DEG C, hot melt section temperature is preferably 330 ~ 350 DEG C, compression section temperature is preferably 310 ~ 330 DEG C, die head temperature is preferably 300 ~ 320 DEG C.
Compared with prior art, the present invention has the following advantages:
1, obtained composition frictional coefficient and frictional dissipation rate low, long product lifecycle after forming process, the present invention adopts metal hydroxides that the open loop of polyimide molecule segment is formed imines and hydroxy-acid group, at a certain temperature with ptfe micropowder carboxylic acids or hydroxyl end groups generation chemical reaction, form chemical bond-linking, improve polyimide and ptfe micropowder is the crocking resistance of based composition and use thereof in packaging, extend the life-span of product after forming process, frictional coefficient is below 0.35, most I reaches 0.09, and frictional dissipation rate is 7.8 × 10
-6mm
3/ below Nm, most I reaches 2.2 × 10
-6mm
3/ Nm;
2, technique is simple, easily realizes industrialization, compared with conventional machining process, further simplify technical process.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
(1) the tetrafluoroethylene homopolymer micro mist 45kg of median size 500nm is taken, Ca (OH)
22.5kg, methyl methacrylate/acrylic acid ester copolymer 2.5kg, at 25 DEG C, mix 0.5h under 100rpm rotating speed, obtain ptfe micropowder Preblend;
(2) the ptfe micropowder Preblend 10kg that polyimide powder (GE Ultem1000) 40kg, step (1) are obtained is taken; at 20 DEG C; after mixing 0.5h under 100rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 250 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 2
(1) the tetrafluoroethylene homopolymer micro mist 46kg of median size 10 μm is claimed, Mg (OH)
22kg, methyl methacrylate/styrol copolymer 2kg, at 20 DEG C, mix 0.7h under 200rpm rotating speed, obtain ptfe micropowder Preblend.
(2) polyimide powder (GE Ultem1000) 41kg is taken; the ptfe micropowder Preblend 9kg that step (1) is obtained; at 15 DEG C; after mixing 0.6h under 200rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 260 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 3
(1) the tetrafluoroethylene homopolymer micro mist 47kg of median size 5 μm is taken, Zn (OH)
21.5kg, vinyl cyanide/styrol copolymer 1.5kg, at 15 DEG C, mix 0.6h under 300rpm rotating speed, obtain ptfe micropowder Preblend.
(2) polyimide powder (GE Ultem1000) 42.5kg is taken; the ptfe micropowder Preblend 7.5kg that step (1) is obtained; at 18 DEG C; after mixing 0.8h under 300rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 270 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 4
(1) the tetrafluoroethylene homopolymer micro mist 48kg of median size 8 μm is taken, Cu (OH)
21kg, methyl methacrylate/acrylic acid ester copolymer 1kg, at 18 DEG C, mix 0.8h under 100rpm rotating speed, obtain ptfe micropowder Preblend.
(2) polyimide powder (GE Ultem1000) 45kg is taken; the ptfe micropowder Preblend 5kg that step (1) is obtained; at 20 DEG C; after mixing 0.8h under 100rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 5
(1) tetrafluoroethylene and chlorotrifluoroethylene micro mist 49kg, the Al (OH) of median size 15 μm is taken
30.5kg, methyl methacrylate/styrol copolymer 0.05kg, at 22 DEG C, mix 0.9h under 200rpm rotating speed, obtains tetrafluoroethylene and the Preblend of chlorotrifluoroethylene micro mist.
(2) polyimide powder (GE Ultem1000) 47kg is taken; the tetrafluoroethylene that step (1) is obtained and chlorotrifluoroethylene micro mist Preblend 3kg; at 22 DEG C; after mixing 0.9h under 200rpm; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 270 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 6
(1) tetrafluoroethylene and chlorotrifluoroethylene micro mist 45kg, the Ca (OH) of median size 12 μm is taken
22.5kg, vinyl cyanide/styrol copolymer 2.5kg, at 25 DEG C, mix 0.5h under 300rpm rotating speed, obtains tetrafluoroethylene and the Preblend of chlorotrifluoroethylene micro mist.
(2) polyimide powder (GE Ultem1000) 49kg is taken; the tetrafluoroethylene that step (1) is obtained and chlorotrifluoroethylene micro mist Preblend 1kg; at 25 DEG C; after mixing 0.5h under 300rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 345 DEG C, 325 DEG C, 320 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 7
(1) tetrafluoroethylene and hexafluoropropylene copolymer micro mist 46kg, the Mg (OH) of median size 2 μm is taken
21kg, Zn (OH)
21kg, methyl methacrylate/acrylic acid ester copolymer 2kg, at 25 DEG C, mix 1h under 200rpm rotating speed, obtains tetrafluoroethylene and the Preblend of hexafluoropropylene copolymer micro mist.
(2) polyimide powder (GE Ultem1000) 40kg is taken; the tetrafluoroethylene that step (1) is obtained and hexafluoropropylene copolymer micro mist Preblend 10kg; at 25 DEG C; after mixing 1h under 200rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 350 DEG C, 330 DEG C, 310 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 8
(1) tetrafluoroethylene and perfluoro propyl vinyl ether copolymer micropowders 47kg, the Cu (OH) of median size 12 μm is taken
20.6kg, Al (OH)
30.6kg, methyl methacrylate/styrol copolymer 1.8kg, at 25 DEG C, mix 1h under 100rpm rotating speed, obtains tetrafluoroethylene and the Preblend of perfluoro propyl vinyl ether copolymer micropowders.
(2) polyimide powder (GE Ultem1000) 42.5kg is taken; the tetrafluoroethylene that step (1) is obtained and perfluoro propyl vinyl ether copolymer micropowders Preblend 7.5kg; at 25 DEG C; after mixing 1h under 100rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 335 DEG C, 315 DEG C, 305 DEG C; granulator granulation is shaping, forms composition.
Embodiment 9
(1) tetrafluoroethylene and perfluoroethylvinyl ether copolymer micropowders 48kg, the Cu (OH) of median size 8 μm is taken
20.5kg, Mg (OH)
20.5kg, methyl methacrylate/acrylic acid ester copolymer 1kg, at 25 DEG C, mix 0.5h under 200rpm rotating speed, obtains tetrafluoroethylene and the Preblend of perfluoroethylvinyl ether copolymer micropowders.
(2) polyimide powder (GE Ultem1000) 45kg is taken; the tetrafluoroethylene that step (1) is obtained and perfluoroethylvinyl ether copolymer micropowders Preblend 5kg; at 25 DEG C; after mixing 0.5h under 200rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 330 DEG C, 310 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Embodiment 10
(1) tetrafluoroethylene and perfluoro methyl vinyl ether copolymer micropowders 49.45kg, the Mg (OH) of median size 3 μm is taken
20.5kg, vinyl cyanide/styrol copolymer 0.05kg, at 25 DEG C, mix 1h under 100rpm rotating speed, obtains tetrafluoroethylene and the Preblend of perfluoro methyl vinyl ether copolymer micropowders.
(2) polyimide powder (GE Ultem1000) 45kg is taken; the tetrafluoroethylene that step (1) is obtained and perfluoro methyl vinyl ether copolymer micropowders Preblend 5kg; at 25 DEG C; after mixing 1h under 100rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Comparative example 1
(1) the tetrafluoroethylene homopolymer micro mist 45kg of median size 500nm is taken, silane coupling agent KH5602.5kg, methyl methacrylate/acrylic acid ester copolymer 2.5kg, at 25 DEG C, mix 0.5h under 100rpm rotating speed, obtain ptfe micropowder Preblend.
(2) the ptfe micropowder Preblend 10kg that polyimide powder (GE Ultem1000) 40kg, step (1) are obtained is taken; at 25 DEG C; after mixing 0.5h under 100rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 250 DEG C, 340 DEG C, 320,300 DEG C; granulator granulation is shaping, obtains composition.
Comparative example 2
(1) take tetrafluoroethylene and the chlorotrifluoroethylene micro mist 49kg of median size 15 μm, methyl methacrylate/styrol copolymer 0.05kg, at 25 DEG C, mixes 0.5h under 200rpm rotating speed, obtains ptfe micropowder Preblend.
(2) polyimide powder (GE Ultem1000) 47kg is taken; the ptfe micropowder Preblend 3kg that step (1) is obtained; at 25 DEG C; after mixing 0.5h under 200rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 270 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Comparative example 3
(1) tetrafluoroethylene and the hexafluoropropylene copolymer micro mist 46kg of median size 2 μm is taken, silane coupling agent KH5602kg, methyl methacrylate/acrylic acid ester copolymer 2kg, at 25 DEG C, mix 1h under 200rpm rotating speed, obtain ptfe micropowder Preblend.
(2) polyimide powder (GE Ultem1000) 40kg is taken; the ptfe micropowder Preblend 10kg that step (1) is obtained; at 25 DEG C; after mixing 1h under 200rpm rotating speed; extrude through twin screw extruder at mixing section, hot melt section, compression section and die head temperature are respectively 280 DEG C, 340 DEG C, 320 DEG C, 300 DEG C; granulator granulation is shaping, obtains composition.
Performance test methods
Frictional behaviour is pressed GB3960-83 with MPX-2000 type friction wear testing machine and is measured, and concrete data see the following form.
The composition frictional behaviour data that embodiment 1 ~ 10 and comparative example 1 ~ 3 obtain
| Performance | Frictional coefficient | Frictional dissipation rate (× 10 -6mm 3/N.m) |
| Embodiment 1 | 0.12 | 3 |
| Embodiment 2 | 0.09 | 2.5 |
| Embodiment 3 | 0.22 | 7.8 |
| Embodiment 4 | 0.31 | 6 |
| Embodiment 5 | 0.35 | 7 |
| Embodiment 6 | 0.1 | 2.2 |
| Embodiment 7 | 0.1 | 2.7 |
| Embodiment 8 | 0.21 | 7.1 |
| Embodiment 9 | 0.33 | 7.7 |
| Embodiment 10 | 0.33 | 5 |
| Comparative example 1 | 0.53 | 10 |
| Comparative example 2 | 0.51 | 14.5 |
| Comparative example 3 | 0.53 | 11.5 |
Claims (7)
1. a preparation method for wear-resisting polyimide and fluoro-containing copolymer composition, is characterized in that comprising the following steps:
(a) by weight, by fluoropolymer micro mist 90 ~ 98.9 parts, metal hydroxides 1 ~ 5 part, processing aid 0.1 ~ 5 part, at 15 ~ 25 DEG C, under 100 ~ 300rpm mix 0.5 ~ 1h, obtain the Preblend of fluoropolymer micro mist;
B () by weight, by polyimide powder 80 ~ 98 parts, the fluoropolymer micro mist Preblend 2 ~ 20 parts that step (a) obtains, at 15 ~ 25 DEG C, after mixing 0.5 ~ 1h under 100 ~ 300rpm, extrude through twin screw extruder, granulating and forming, obtain wear-resisting polyimide and fluoro-containing copolymer composition.
2. the preparation method of wear-resisting polyimide according to claim 1 and fluoro-containing copolymer composition, is characterized in that described fluoropolymer micro mist is the one in proplast micro mist, tetrafluoroethylene and chlorotrifluoroethylene micro mist, tetrafluoroethylene and vinylidene fluoride copolymers micro mist, tetrafluoroethylene and hexafluoropropylene copolymer micro mist, tetrafluoroethylene and perfluoro propyl vinyl ether copolymer micropowders, tetrafluoroethylene and perfluoroethylvinyl ether copolymer micropowders, tetrafluoroethylene and perfluoro methyl vinyl ether copolymer micropowders.
3. the preparation method of wear-resisting polyimide according to claim 1 and fluoro-containing copolymer composition, is characterized in that described fluoropolymer micro mist median size is 500nm ~ 15 μm.
4. the preparation method of wear-resisting polyimide according to claim 3 and fluoro-containing copolymer composition, is characterized in that described fluoropolymer micro mist median size is 2 ~ 8 μm.
5. the preparation method of wear-resisting polyimide according to claim 1 and fluoro-containing copolymer composition, is characterized in that described metal hydroxides is Ca (OH)
2, Mg (OH)
2, Zn (OH)
2, Cu (OH)
2, Al (OH)
3in one or both mixture.
6. the preparation method of wear-resisting polyimide according to claim 1 and fluoro-containing copolymer composition, is characterized in that described processing aid is the one in methyl methacrylate/acrylic acid ester copolymer, methyl methacrylate/styrol copolymer, vinyl cyanide/styrol copolymer.
7. the preparation method of wear-resisting polyimide according to claim 1 and fluoro-containing copolymer composition, it is characterized in that the mixing section temperature of described twin screw extruder is 250 ~ 280 DEG C, hot melt section temperature is 330 ~ 350 DEG C, compression section temperature is 310 ~ 330 DEG C, and die head temperature is 300 ~ 320 DEG C.
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|---|---|---|---|---|
| EP0126781A1 (en) * | 1982-03-18 | 1984-12-05 | General Electric Company | Polyetherimide-fluorinated polyolefin blends |
| EP0251741A2 (en) * | 1986-06-30 | 1988-01-07 | MITSUI TOATSU CHEMICALS, Inc. | Polyimide resin composition |
| CN1186827A (en) * | 1996-12-24 | 1998-07-08 | 中国科学院兰州化学物理研究所 | Polyimide self lubricating composite material |
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN1602342A (en) * | 2001-07-26 | 2005-03-30 | 索尔维先进聚合物有限责任公司 | Improved polyamide-imide molding resins and methods for their preparation |
| CN102352095A (en) * | 2003-12-30 | 2012-02-15 | 沙伯基础创新塑料知识产权有限公司 | Polymer compositions, method of manufacture, and articles formed therefrom |
-
2015
- 2015-03-20 CN CN201510124243.0A patent/CN104761915B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0126781A1 (en) * | 1982-03-18 | 1984-12-05 | General Electric Company | Polyetherimide-fluorinated polyolefin blends |
| EP0251741A2 (en) * | 1986-06-30 | 1988-01-07 | MITSUI TOATSU CHEMICALS, Inc. | Polyimide resin composition |
| CN1186827A (en) * | 1996-12-24 | 1998-07-08 | 中国科学院兰州化学物理研究所 | Polyimide self lubricating composite material |
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN1602342A (en) * | 2001-07-26 | 2005-03-30 | 索尔维先进聚合物有限责任公司 | Improved polyamide-imide molding resins and methods for their preparation |
| CN102352095A (en) * | 2003-12-30 | 2012-02-15 | 沙伯基础创新塑料知识产权有限公司 | Polymer compositions, method of manufacture, and articles formed therefrom |
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