CN104650586A - Epoxy resin modified polyphenylene sulfide composite material and preparation method thereof - Google Patents
Epoxy resin modified polyphenylene sulfide composite material and preparation method thereof Download PDFInfo
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- CN104650586A CN104650586A CN201510078277.0A CN201510078277A CN104650586A CN 104650586 A CN104650586 A CN 104650586A CN 201510078277 A CN201510078277 A CN 201510078277A CN 104650586 A CN104650586 A CN 104650586A
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- epoxy resin
- polyphenylene sulfide
- pps
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses an epoxy resin modified polyphenylene sulfide (PPS) composite material and a preparation method thereof and belongs to the technical field of high-molecular composite materials. PPS particle material is subjected to surface treatment by using epoxy resin and a coupling agent and then is ball-milled to obtain modified PPS powder; the modified PPS powder and inorganic powder filler are uniformly mixed by using a high-speed mixer, and then a double-screw extruder is used for performing reactive extrusion granulation on the mixture to obtain the PPS composite material. The PPS composite material consists of the following components: 55-95 percent of polyphenylene sulfide resin, 2-5 percent of epoxy resin, 0.1-40 percent of inorganic powder filler and 0.2-2 percent of coupling agent. Compared with PPS, the composite material is greatly improved in strength and toughness.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to the Technology that p-poly-phenyl thioether carries out modification.
Background technology
Polyphenylene sulfide (PPS), polyether-ether-ketone (PEEK), polysulfones (PSF), polyimide (PI), polyarylester (PAR) and liquid crystalline polymers (LCP) are called as 6 large special engineering plastics.Polyphenylene sulfide (PPS) over-all properties is superior, has excellent heat-resisting, corrosion resistance nature, and less than 200 DEG C are insoluble to any solvent.It also has comparatively high flame resistance, and do not add fire retardant and just can reach UL94 V0 level, good stability of the dimension, under hot environment, after moisture absorption, size is almost constant, has fabulous bond properties and excellent processing characteristics.Therefore, PPS has become the first kind of special engineering plastics, is widely used in the fields such as electronics, electrical equipment, automobile, aerospace.But PPS is Shortcomings part also, the fragility as pure PPS goods is comparatively large, toughness is poor, rigidity and insufficient strength high, price is higher in addition, which limits the application of PPS.So, need to strengthen and toughening modifying PPS.The main method strengthened PPS is Inorganic Fillers Filled, as added glass and carbon fiber.The main method toughness reinforcing to PPS has chemical modification and physically modified.Chemical structure modification introduces modified monomer in PPS molecular chain, and change the molecular chain structure of PPS, the toughening modifying Be very effective of chemical toughening modification, weak point to pass through some chemical reactions, the bad control of process.Physically modified adds another kind of elastomeric component in the base, but do not change molecular chain structure, by forming the excellent co-mixing system of function, reaches toughness reinforcing object.The study general of current MODIFIED PP S concentrates on PPS and glass fibre, mineral filler, carbon fiber or other polymer blending modifications, thus the performance of balanced each polymkeric substance and inorganics component, obtain the matrix material of excellent combination property.Meanwhile, blendedly also can give PPS property, as anti-oilness, electroconductibility, become functionalized polymer.
The molecular structure of epoxy resin be with in molecular chain containing active epoxide group for feature, epoxide group can be positioned at the end of molecular chain, centre or structure circlewise.The toughening mechanism of epoxy resin to PPS is that the epoxide group of epoxy resin with-SH group in PPS, following chain extending reaction can occur, result introduces flexible chain on the PPS chain of rigidity, reduce the crystallinity of PPS, result makes the toughness of PPS increase considerably.
Epoxy resin has excellent adhesiveproperties to metal and non-metallic material simultaneously, the consistency of inorganic powdered filler and PPS matrix can be increased, promote dispersed in PPS matrix, therefore, epoxy resin can play the effect of interfacial compatibilizer in PPS composite system.Therefore, epoxy resin modification polyphenyl thioether composite material has excellent intensity and toughness.
Summary of the invention
The present invention seeks to the modified polyphenyl thioether matrix material proposing a kind of high strength, high tenacity.
Matrix material of the present invention is made up of polyphenylene sulfide, epoxy resin, inorganic powdered filler and coupling agent, described polyphenylene sulfide accounts for 55% ~ 95% of matrix material total mass, epoxy resin accounts for 2% ~ 5% of matrix material total mass, inorganic powdered filler accounts for 0.1% ~ 40% of matrix material total mass, and coupling agent accounts for 0.2% ~ 2% of matrix material total mass.
Compare PPS tensile strength, elongation at break and toughness through modified matrix material to have had and significantly promote.
Described inorganic powdered filler is the one in halloysite, short glass fiber, carbon nanotube or carbon fiber.The filling of these inorganic powdered filler can give the more excellent intensity of matrix material and toughness, can improve the thermostability of matrix material simultaneously.
Described coupling agent is the one in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.The use of coupling agent can improve interfacial adhesion between PPS and inorganic powdered filler, and then improves the mechanical mechanics property of matrix material.
Described epoxy resin model is the one in E-51, E-44.The epoxy resin presenting liquid state under normal temperature has higher oxirane value, has more and PPS and reacts toughness reinforcing active group.
The present invention also proposes the preparation method of above matrix material.
Its technical scheme is: dry under 60 DEG C of conditions after epoxy resin being dissolved in solvent with after coupling agent and dry polyphenylene sulfide Homogeneous phase mixing, then polyphenylene sulfide modified powder is obtained through grinding, then through twin screw extruder extruding pelletization after polyphenylene sulfide modified powder is mixed with inorganic powdered filler; The polyphenylene sulfide of described drying accounts for 55% ~ 95% of total charging capacity, and described epoxy resin accounts for 2% ~ 5% of total charging capacity, and coupling agent accounts for 0.2% ~ 2% of total charging capacity, and inorganic powdered filler accounts for 0.1% ~ 40% of total charging capacity.
The present invention is directed to the unmanageable shortcoming of chemical modification Toughened PP S process, innovatively adopt epoxy resin modification PPS, utilize reactively blending technology to realize chemical modification Toughened PP S.Utilize the functional group on epoxy molecule on this basis, and coupling technology increases the interface compatibility of inorganic powdered filler and PPS matrix, to obtain inorganic powdered filler finely dispersed compound system in polymeric matrix, preparation technology is simple, with low cost, low for equipment requirements.
Solvent of the present invention be in acetone, ether, ethanol, toluene at least any one, solvent load is 10 times of epoxy resin and coupling agent total mass.Adopt quality 10 doubly can soak PPS pellet well to the solvent of organic modifiers, make PPS surface modification more even.
Described inorganic powdered filler be in halloysite, short glass fiber, carbon nanotube or carbon fiber at least any one.The filling of these inorganic powdered filler can give the more excellent intensity of matrix material and toughness, can improve the thermostability of matrix material simultaneously.
Described coupling agent be in γ-aminopropyl triethoxysilane (KH-550), γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) at least any one.The use of coupling agent can improve interfacial adhesion between PPS and inorganic powdered filler, and then improves the mechanical mechanics property of matrix material.
Described epoxy resin model be in E-51, E-44 at least any one.The epoxy resin presenting liquid state under normal temperature has higher oxirane value, has more and PPS and reacts toughness reinforcing active group.
The polyphenylene sulfide modified powder mixed with inorganic powdered filler is the polyphenylene sulfide modified powder obtained through 300 mesh sieves.Polyphenylene sulfide modified powder reaches certain fineness, the degree of uniformity of guarantee modification.
In addition, in described twin screw extruder, the temperature in 1st ~ 9 district is respectively 270 ~ 280 DEG C, 270 ~ 280 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, the head temperature of twin screw extruder is 290 ~ 300 DEG C.The temperature range of control Ge Duan district and head, to guarantee that reactive extrursion is evenly blended, and is convenient to matrix material granulation.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1:
(1) polyphenylene sulfide (lot number I) is stand-by after dry 2 ~ 4h under 110 DEG C of environment.
(2) 5kg model be E-51 55kg acetone solution used for epoxy resin after, add 0.5kg coupling agent γ-aminopropyl triethoxysilane (KH-550) and dried 100kg polyphenylene sulfide, stir and be placed on 60 DEG C of forced air drying 6 h.In step, solvent acetone is volatilized.
(3), after the mixture that step (2) obtains being added grinding in ball grinder 40 ~ 60 min, the MODIFIED PP S powder of 300 mesh sieves must be.
(4) the MODIFIED PP S powder and 0.25kg multi-walled carbon nano-tubes of crossing 300 mesh sieves are added mixing 1 ~ 2min in 5000 revs/min of high-speed mixers.
(5) compound of step (4) gained is joined in twin screw extruder, extruding pelletization, and the temperature controlling 1st ~ 9 district in twin screw extruder is respectively 270 ~ 280 DEG C, 270 ~ 280 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, the head temperature of twin screw extruder is 290 ~ 300 DEG C.
(6) composite particles that (5) obtain is injection molded into test bars after dry 3h at 130 DEG C.The temperature of injection moulding machine is 290 ~ 320 DEG C, and injection pressure is 60MPa, 15 seconds inject time, die temperature 90 DEG C.The mechanical experimental results of testing bar is as shown in table 1.
Table 1 embodiment 1 mechanical experimental results
Compare polyphenylene sulfide (lot number I), the matrix material obtained through embodiment 1 production has more excellent mechanical mechanics property.
Embodiment 2:
(1) polyphenylene sulfide (lot number II) is stand-by after dry 2 ~ 4h under 110 DEG C of environment.
(2) 5kg model be E-44 55kg acetone solution used for epoxy resin after, add 0.5kg coupling agent KH-550 and dried 100kg polyphenylene sulfide, stir and be placed on 60 DEG C of forced air drying 6 h.In step, solvent acetone is volatilized.
(3), after the mixture that step (2) obtains being added grinding in ball grinder 40 ~ 60 min, the MODIFIED PP S powder of 300 mesh sieves must be.
(4) the MODIFIED PP S powder and 44.5kg short glass fiber of crossing 300 mesh sieves are added mixing 1 ~ 2min in 5000 revs/min of high-speed mixers.
(5) compound of step (4) gained is joined in twin screw extruder, extruding pelletization, and the temperature controlling 1st ~ 9 district in twin screw extruder is respectively 270 ~ 280 DEG C, 270 ~ 280 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, the head temperature of twin screw extruder is 290 ~ 300 DEG C.
(6) composite particles (5) obtained is injection molded into test bars after dry 3 h at 130 DEG C.The temperature of injection moulding machine is 290 ~ 320 DEG C, and injection pressure is 60MPa, 15 seconds inject time, die temperature 90 DEG C.Test bars mechanical experimental results is as shown in table 2.
Table 2 embodiment 2 mechanical experimental results
Embodiment 2 result shows, although be filled with the glass of 44.5 parts, matrix material comparatively PPS toughness remains unchanged substantially, and tensile strength adds 40%, and preparation cost reduces greatly.
Above solvent acetone is replaced by ether, ethanol or toluene and is used.
Inorganic powdered filler short glass fiber, carbon nanotube can be replaced and adopt halloysite or carbon fiber.
Coupling agent also can adopt γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an epoxy resin modification polyphenyl thioether composite material, it is characterized in that: matrix material is made up of polyphenylene sulfide, epoxy resin, inorganic powdered filler and coupling agent, described polyphenylene sulfide accounts for 55% ~ 95% of matrix material total mass, epoxy resin accounts for 2% ~ 5% of matrix material total mass, inorganic powdered filler accounts for 0.1% ~ 40% of matrix material total mass, and coupling agent accounts for 0.2% ~ 2% of matrix material total mass.
2. matrix material according to claim 1, is characterized in that: described inorganic powdered filler is the one in halloysite, short glass fiber, carbon nanotube or carbon fiber.
3. matrix material according to claim 1, is characterized in that: described coupling agent is the one in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.
4. matrix material according to claim 1, is characterized in that: described epoxy resin model is the one in E-51, E-44.
5. the preparation method of epoxy resin modification polyphenyl thioether composite material as claimed in claim 1, it is characterized in that: dry under 60 DEG C of conditions after epoxy resin being dissolved in solvent with after coupling agent and dry polyphenylene sulfide Homogeneous phase mixing, then polyphenylene sulfide modified powder is obtained through grinding, then through twin screw extruder extruding pelletization after polyphenylene sulfide modified powder is mixed with inorganic powdered filler; The polyphenylene sulfide of described drying accounts for 55% ~ 95% of total charging capacity, and described epoxy resin accounts for 2% ~ 5% of total charging capacity, and coupling agent accounts for 0.2% ~ 2% of total charging capacity, and inorganic powdered filler accounts for 0.1% ~ 40% of total charging capacity.
6. preparation method according to claim 5, is characterized in that: described solvent be in acetone, ether, ethanol, toluene at least any one, solvent load is 10 times of epoxy resin and coupling agent total mass.
7. preparation method according to claim 5 or 6, is characterized in that: the polyphenylene sulfide modified powder mixed with inorganic powdered filler is the polyphenylene sulfide modified powder obtained through 300 mesh sieves.
8. preparation method according to claim 5 or 6, it is characterized in that: in described twin screw extruder, the temperature in 1st ~ 9 district is respectively 270 ~ 280 DEG C, 270 ~ 280 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 285 ~ 295 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, 300 ~ 310 DEG C, the head temperature of twin screw extruder is 290 ~ 300 DEG C.
9. preparation method according to claim 5 or 6, is characterized in that: described inorganic powdered filler be in halloysite, short glass fiber, carbon nanotube or carbon fiber at least any one.
10. preparation method according to claim 5 or 6, is characterized in that: described coupling agent be in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane at least any one; Described epoxy resin model be in E-51, E-44 at least any one.
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Cited By (9)
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|---|---|---|---|---|
| CN105670287A (en) * | 2016-04-17 | 2016-06-15 | 刘家容 | Preparation method of impact-resistant high-toughness carbon fiber composite material |
| CN106317767A (en) * | 2016-08-22 | 2017-01-11 | 苏州聚冠复合材料有限公司 | Preparation method of ultrahigh-conductivity 3D printing carbon fiber composite wire |
| CN107286657A (en) * | 2017-08-08 | 2017-10-24 | 合肥安力电力工程有限公司 | A kind of noise abatement, anticorrosive high and low voltage electric distribution device shell and preparation method |
| CN109578709A (en) * | 2018-11-28 | 2019-04-05 | 盐城市瑞通塑胶有限公司 | A kind of heat resisting and pressure resisting pipeline |
| CN109694575A (en) * | 2018-11-28 | 2019-04-30 | 江苏欧瑞达新材料科技有限公司 | A kind of good PPS of epoxy resin caking property |
| CN110938308A (en) * | 2019-12-24 | 2020-03-31 | 罗勇 | Preparation method of polyphenylene sulfide engineering plastic |
| CN112063334A (en) * | 2020-09-09 | 2020-12-11 | 江苏艾森半导体材料股份有限公司 | Modified polyphenylene sulfide light diffusant for LED epoxy encapsulation and preparation method thereof |
| CN113913014A (en) * | 2021-10-27 | 2022-01-11 | 长沙新材料产业研究院有限公司 | Composite material, bearing retainer and preparation method thereof |
| CN115232426A (en) * | 2022-08-24 | 2022-10-25 | 四川金和成科技有限公司 | Polyphenylene sulfide resin composite material and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670287A (en) * | 2016-04-17 | 2016-06-15 | 刘家容 | Preparation method of impact-resistant high-toughness carbon fiber composite material |
| CN106317767A (en) * | 2016-08-22 | 2017-01-11 | 苏州聚冠复合材料有限公司 | Preparation method of ultrahigh-conductivity 3D printing carbon fiber composite wire |
| CN107286657A (en) * | 2017-08-08 | 2017-10-24 | 合肥安力电力工程有限公司 | A kind of noise abatement, anticorrosive high and low voltage electric distribution device shell and preparation method |
| CN109578709A (en) * | 2018-11-28 | 2019-04-05 | 盐城市瑞通塑胶有限公司 | A kind of heat resisting and pressure resisting pipeline |
| CN109694575A (en) * | 2018-11-28 | 2019-04-30 | 江苏欧瑞达新材料科技有限公司 | A kind of good PPS of epoxy resin caking property |
| CN110938308A (en) * | 2019-12-24 | 2020-03-31 | 罗勇 | Preparation method of polyphenylene sulfide engineering plastic |
| CN112063334A (en) * | 2020-09-09 | 2020-12-11 | 江苏艾森半导体材料股份有限公司 | Modified polyphenylene sulfide light diffusant for LED epoxy encapsulation and preparation method thereof |
| CN112063334B (en) * | 2020-09-09 | 2021-10-08 | 江苏艾森半导体材料股份有限公司 | Modified polyphenylene sulfide light diffusant for LED epoxy encapsulation and preparation method thereof |
| CN113913014A (en) * | 2021-10-27 | 2022-01-11 | 长沙新材料产业研究院有限公司 | Composite material, bearing retainer and preparation method thereof |
| CN113913014B (en) * | 2021-10-27 | 2024-02-09 | 航天科工(长沙)新材料研究院有限公司 | Composite material, bearing retainer and preparation method thereof |
| CN115232426A (en) * | 2022-08-24 | 2022-10-25 | 四川金和成科技有限公司 | Polyphenylene sulfide resin composite material and preparation method thereof |
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