CN103509343A - Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof - Google Patents
Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof Download PDFInfo
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- CN103509343A CN103509343A CN201210215944.1A CN201210215944A CN103509343A CN 103509343 A CN103509343 A CN 103509343A CN 201210215944 A CN201210215944 A CN 201210215944A CN 103509343 A CN103509343 A CN 103509343A
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- composite material
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- glass fiber
- polyphenylene sulfide
- polyphenyl thioether
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and a preparation method thereof. The composite material comprises the following components by weight percent: 5%-60% of polyphenylene sulfide, 5%-30% of polyphenyl ether, 10%-60% of flat glass fiber, 0%-10% of mineral filler, 0.1%-3% of coupling agent and 0.1%-2% of processing agent. The preparation method comprises the following steps of: (a) drying polyphenylene sulfide resin and polyphenyl ether resin in an oven with a dehumidification drying machine at the temperatures of 140-160 DEG C and 120-140 DEG C for 3-5 hours, respectively; (b) weighing dried polyphenylene sulfide resin and polyphenyl ether resin and mixing together; (c) weighing the mineral filler, the coupling agent and the processing agent and adding into a high-speed mixer for high-speed premixing; and (d) sequentially adding a mixture in step (b), a mixture in step (c) and the weighed flat glass fiber into a double-screw extruder for pelletizing by melt extrusion.
Description
[technical field]
The present invention relates to a kind of polyphenyl thioether/polyphenylether composite material, be specifically related to a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof.
[background technology]
Polyphenylene sulfide (PPS) is a kind of novel crystallinity High performance plastic resin, thermotolerance is better, possesses excellent chemical stability, and owing to possessing high strength, high rigidity, under hot conditions, rigidity seldom reduces, there is outstanding fatigue performance and creep-resistant property, so better mechanical property.Yet polyphenylene sulfide is very easily mobile, simple resin is difficult to injection moulding, and glass fibre strengthens and fills the rear coarse low in glossiness of product surface, and shock strength is poor, goods embrittlement, and welding strength is bad, and its coating and tint permanence are undesirable.
Polyphenylene oxide (PPO) is amorphous material, has extraordinary dimensional stability and mechanical property, and polyphenylene oxide density is 1.08g/cm
3, in engineering plastics, be minimum.Yet when using separately, there is the defect that resistance to fatigue is poor and stress cracking resistance is poor in polyphenylene oxide.
At present, polyphenylene sulfide and polyphenylene oxide composite material adopt filamentary material to carry out enhancement process mostly, mainly add glass (GF), carbon fine (CF) and mineral etc.The glass before adding is typical circular cross-sectional shape, yet adding polyphenylene sulfide and polyphenylene oxide composite material after common glass strengthens is not very desirable in each physicals, and the problem that easily occurs warpage when forming process, what particularly on ultra-thin, show is particularly evident, has limited its application.
[summary of the invention]
In view of the above problems, the object of the invention is to develop a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, this fiberglass enhanced polyphenyl thioether/polyphenylether composite material can further improve the physicals of polyphenyl thioether/polyphenylether composite material, and the warpage issues occurring can improve forming process time.
In order to achieve the above object, fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present invention, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 5～60%;
Polyphenylene oxide 5～30%;
Flat glass fiber 10～60%;
Mineral filler 0～10%;
Coupling agent 0.1～3%;
Processing aid 0.1～2%.
Especially, above-mentioned polyphenylene sulfide viscosity is 50～150Pas.
Especially, in above-mentioned matrix material, the weight percentage containing polyphenylene oxide is 8～15%.
Especially, the flat ratio of above-mentioned flat glass fiber is 0.1～0.5, is preferably 0.2～0.3.
Especially, the minor axis in the cross section of above-mentioned flat glass fiber is 0.5～25um, and the major diameter in cross section is 1.0～250um.
Especially, above-mentioned mineral filler is a kind of in talcum powder, barium sulfate or calcium carbonate.
Especially, above-mentioned coupling agent is silane coupling agent.
Especially, above-mentioned processing aid is a kind of, two or more the mixture in lipid acid, calcium stearate, Zinic stearas, silicone powder.
In addition, the present invention also provides a kind of preparation method of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, and for the preparation of above-mentioned fiberglass enhanced polyphenyl thioether/polyphenylether composite material, the method comprises the following steps:
(a) by polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours;
(b) take dried polyphenylene sulfide and polyphenylene oxide resin and mix;
(c) take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix;
(d) mixture in mixture, step (c) in above-mentioned steps (b) and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Compared to prior art, fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present invention and preparation method thereof, by using the fiberglass enhanced polyphenyl thioether/polyphenylether composite material of flattened, can further improve the physicals of polyphenyl thioether/polyphenylether composite material, the warpage issues occurring while improving forming process, makes it more be widely used in the fields such as electronics, electrical equipment, automobile and aerospace.
[embodiment]
For object of the present invention, function and technique means are had to further understanding, existing as follows to the detailed description of the invention in conjunction with specific embodiments.
The starting material that use in comparative example and embodiment are as follows:
Polyphenylene sulfide is that Deyang, Sichuan company produces, and the trade mark is hb-crossDL.
Polyphenylene oxide WeiGE company produces, and the trade mark is N300.
Flat glass fiber is that Nittobo company produces, and the trade mark is 962S.
Circular glass fiber is that megalith company produces, and the trade mark is 540.
Mineral filler is that elite company produces, and the trade mark is SK-6800B.
Coupling agent adopts KH560.
Embodiment 1
The fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present embodiment, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 58.7%;
Polyphenylene oxide 5%;
Flat glass fiber 30%;
Mineral filler 5%;
Coupling agent 0.3%;
Processing aid 1%.
By polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours; Take dried polyphenylene sulfide and polyphenylene oxide resin and mix; Take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix; All mixtures in above-mentioned steps and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Comparative example 1
Comparative example 1 is by the circular glass fiber of the weight percentage such as flat glass fiber is changed in embodiment 1; All the other components and weight percentage are all identical, then with same preparation method's preparation.
Embodiment 2
The fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present embodiment, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 28.5%;
Polyphenylene oxide 5%;
Flat glass fiber 60%;
Mineral filler 5%;
Coupling agent 0.5%;
Processing aid 1%.
By polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours; Take dried polyphenylene sulfide and polyphenylene oxide resin and mix; Take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix; All mixtures in above-mentioned steps and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Comparative example 2
Comparative example 2 is by the circular glass fiber of the weight percentage such as flat glass fiber is changed in embodiment 2; All the other components and weight percentage are all identical, then with same preparation method's preparation.
Embodiment 3
The fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present embodiment, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 38.7%;
Polyphenylene oxide 10%;
Flat glass fiber 45%;
Mineral filler 5%;
Coupling agent 0.3%;
Processing aid 1%.
By polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours; Take dried polyphenylene sulfide and polyphenylene oxide resin and mix; Take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix; All mixtures in above-mentioned steps and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Comparative example 3
Comparative example 3 is by the circular glass fiber of the weight percentage such as flat glass fiber is changed in embodiment 3; All the other components and weight percentage are all identical, then with same preparation method's preparation.
Embodiment 4
The fiberglass enhanced polyphenyl thioether/polyphenylether composite material of the present embodiment, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 36.7%;
Polyphenylene oxide 12%;
Flat glass fiber 45%;
Mineral filler 5%;
Coupling agent 0.3%;
Processing aid 1%.
By polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours; Take dried polyphenylene sulfide and polyphenylene oxide resin and mix; Take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix; All mixtures in above-mentioned steps and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Comparative example 4
Comparative example 4 is by the circular glass fiber of the weight percentage such as flat glass fiber is changed in embodiment 4; All the other components and weight percentage are all identical, then with same preparation method's preparation.
Each embodiment and comparative example melt extrude after granulation above, then injection moulding ASTM standard testing batten on injection moulding machine, press the mechanical property of ASTM standard testing resulting materials, wherein according to ASTM D638 test tensile strength, according to ASTM D790 test flexural strength and modulus in flexure, according to ASTM D256 test shock strength, and estimate products formed warpage degree, test result is as shown in table 1:
Table 1: embodiment and comparative example test result
By table 1, draw: in embodiment, adopt the glass fibre of flattened to compare with adopting the glass fibre of circular section shape in comparative example, tensile strength, flexural strength, modulus in flexure and shock strength at the matrix material obtaining have all improved 10%～30%, also improve the defect of products formed warpage, shown the superiority of flat glass fiber; And in embodiment according to the flame retardant properties of UL-94 standard testing matrix material, in the situation that not dosing any fire retardant, reach UL94-V0 grade.
In addition, the flat ratio of flat glass fiber is more than 0.2, flexural strength and shock strength can maintain higher level, if flat glass fiber cross section is too thin, more difficult the obtaining sometimes that spin of glass fibre, if contrary its cross section is too thick, the reinforced effects reducing as strongthener due to the contact area with resin can reduce, therefore, contriver is 0.2～0.3 through concentrated research flat ratio, cross section minor axis is 0.5～25um, and when the major diameter in cross section is 1.0～250um, reinforced effects is best.
Therefore, use flat glass fiber to strengthen polyphenyl thioether/polyphenylether composite material, can further improve the physicals of polyphenyl thioether/polyphenylether composite material, improve the defect of products formed warpage, make it more be widely used in the fields such as electronics, electrical equipment, automobile and aerospace.
Claims (10)
1. a fiberglass enhanced polyphenyl thioether/polyphenylether composite material, is characterized in that, percentage ratio calculates by weight, and it comprises following component:
Polyphenylene sulfide 5～60%;
Polyphenylene oxide 5～30%;
Flat glass fiber 10～60%;
Mineral filler 0～10%;
Coupling agent 0.1～3%;
Processing aid 0.1～2%.
2. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, above-mentioned polyphenylene sulfide viscosity is 50～150Pas.
3. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, the weight percentage containing polyphenylene oxide in above-mentioned matrix material is 8～15%.
4. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, the flat ratio of above-mentioned flat glass fiber is 0.1～0.5.
5. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 4, is characterized in that, the flat ratio of above-mentioned flat glass fiber is 0.2～0.3.
6. according to the fiberglass enhanced polyphenyl thioether/polyphenylether composite material described in claim 1,4 or 5, it is characterized in that, the minor axis in the cross section of above-mentioned flat glass fiber is 0.5～25um, and the major diameter in cross section is 1.0～250um.
7. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, above-mentioned mineral filler is a kind of in talcum powder, barium sulfate or calcium carbonate.
8. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, above-mentioned coupling agent is silane coupling agent.
9. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1, is characterized in that, above-mentioned processing aid is a kind of, two or more the mixture in lipid acid, calcium stearate, Zinic stearas, silicone powder.
10. a preparation method for fiberglass enhanced polyphenyl thioether/polyphenylether composite material, is characterized in that, the method comprises the following steps:
(a) by polyphenylene sulfide and polyphenylene oxide resin respectively at the temperature of 140～160 ℃ and 120～140 ℃ in dehumidifying heat pump baking oven dry 3～5 hours;
(b) take dried polyphenylene sulfide and polyphenylene oxide resin and mix;
(c) take mineral filler, coupling agent and processing aid and join high-speed mixer high speed premix;
(d) mixture in mixture, step (c) in above-mentioned steps (b) and the flat glass fiber that takes are joined successively and on twin screw extruder, melt extrude granulation, each interval temperature of twin screw extruder is respectively: 190～280 ℃, an interval, two 240～290 ℃, intervals, three 240～290 ℃, intervals, four 240～300 ℃, intervals, five 240～310 ℃, intervals, six 240～310 ℃, intervals, seven 240～310 ℃, intervals, eight 240～310 ℃, intervals, nine 240～310 ℃, intervals, head temperature is 270～310 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210215944.1A CN103509343A (en) | 2012-06-28 | 2012-06-28 | Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210215944.1A CN103509343A (en) | 2012-06-28 | 2012-06-28 | Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof |
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| CN103509343A true CN103509343A (en) | 2014-01-15 |
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| CN201210215944.1A Pending CN103509343A (en) | 2012-06-28 | 2012-06-28 | Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264767A (en) * | 2018-02-07 | 2018-07-10 | 深圳华力兴新材料股份有限公司 | A kind of NMT technologies PPS/PPO alloys engineering plastics and preparation method |
| CN111849162A (en) * | 2019-04-24 | 2020-10-30 | 旭化成株式会社 | Thin-walled component and container |
| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553537A (en) * | 2006-09-25 | 2009-10-07 | 出光兴产株式会社 | Polyphenylene sulfide resin molded article |
| CN101768359A (en) * | 2008-12-31 | 2010-07-07 | 深圳市科聚新材料有限公司 | Fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof |
-
2012
- 2012-06-28 CN CN201210215944.1A patent/CN103509343A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553537A (en) * | 2006-09-25 | 2009-10-07 | 出光兴产株式会社 | Polyphenylene sulfide resin molded article |
| CN101768359A (en) * | 2008-12-31 | 2010-07-07 | 深圳市科聚新材料有限公司 | Fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264767A (en) * | 2018-02-07 | 2018-07-10 | 深圳华力兴新材料股份有限公司 | A kind of NMT technologies PPS/PPO alloys engineering plastics and preparation method |
| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
| CN111849162A (en) * | 2019-04-24 | 2020-10-30 | 旭化成株式会社 | Thin-walled component and container |
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