CN101768359B - Fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof - Google Patents
Fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof Download PDFInfo
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- CN101768359B CN101768359B CN2008102419813A CN200810241981A CN101768359B CN 101768359 B CN101768359 B CN 101768359B CN 2008102419813 A CN2008102419813 A CN 2008102419813A CN 200810241981 A CN200810241981 A CN 200810241981A CN 101768359 B CN101768359 B CN 101768359B
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- Prior art keywords
- polyphenyl thioether
- composite material
- polyphenylether
- fiberglass
- fiberglass enhanced
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- 229920006389 polyphenyl polymer Polymers 0.000 title claims abstract description 35
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 31
- 239000011152 fibreglass Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 13
- 239000012764 mineral filler Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 48
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 48
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 26
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 26
- -1 pentaerythritol ester Chemical class 0.000 claims description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000005422 blasting Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/92—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
- B29C2948/92514—Pressure
-
- 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
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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 discloses a fiberglass enhanced polyphenyl thioether/polyphenylether composite material and a preparation method thereof. The composite material is mainly prepared by the following raw materials: polyphenyl thioether, polyphenylether, fiberglass, mineral filler, a compatibility agent, an antioxidant and a processing aid. The preparation method of the fiberglass enhanced polyphenyl thioether/polyphenylether composite material comprises the following steps of: (a) firstly, respectively blasting and drying polyphenyl thioether resin and polyphenylether resin; (b) weighting the polyphenyl thioether resin and the polyphenylether resin which are dried, the mineral filler, the compatibility agent, the antioxidant and the processing aid; (c) mixing the dry materials in the step (b) to obtain a compound; and (d) adding the compound in the step (c) and the fiberglass to a double screw extruder for melt blending and pelleting. The fiberglass enhanced polyphenyl thioether/polyphenylether composite material can unconspicuously lower the temperature-resistant level and the rigidity of the polyphenyl thioether resin, further improve the molding accuracy of the polyphenyl thioether resin and decrease the cost.
Description
Technical field
The invention belongs to technical field of polymer materials; Relate to a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material and preparation method thereof; Fiberglass enhanced polyphenyl thioether/polyphenylether composite material is applicable to fields such as electronics, electrical equipment, automobile, aerospace, can make the material of parts around the motor car engine, connector etc.
Background technology
Polyphenylene sulfide (PPS) is a kind of special engineering plastics of excellent combination property.The study on the synthesis of PPS starts from the sixties, is called polyphenylene sulphide again or gathers the phenylene thioether, only contains a base polymer of phenylene and sulfide group in the molecular chain.Polyphenylene sulfide itself has the performance of many excellences: the thermotolerance of 1, giving prominence to: short term thermal modification temperature is up to 260 degree after the modification, and long-term use temperature continuously is 200～240 degree, makes one of the highest thermally-stabilised resin in the thermoplastics; 2, chemical stability: PPS is insoluble to any known solvent below 200 degree, be considered to a kind of good chemical resistance material that is only second to tetrafluoroethylene; 3, mechanical property: the PPS resin has HS, high rigidity, and rigidity seldom reduces under the hot conditions, has outstanding fatigue performance and creep-resistant property; 4, flame retardant properties: the flame retardant resistance of PPS resin is to determine that by itself chemical structure the fire-retardant rank of its vertical combustion can reach UL 94V-0 level, and oxygen index reaches 44～53; 5, dimensional stability: under the hot environment, size is almost constant after the moisture absorption, and dimensional stability surpasses thermosetting resin.Because PPS has many excellent properties, is widely used at electronics, electrical equipment, automobile, precision optical machinery, aerospace, nuclear power, petrochemical complex and food processing field.But because PPS also has some shortcomings: 1, very easily mobile, simple resin is difficult to injection moulding; 2, spun glass enhancing and filling back product surface are coarse, low in glossiness; 3, cost is high, compares price with general engineering plastic and exceeds twice; 4, shock strength is poor, the goods embrittlement, and heat seal strength is bad; 5, because PPS has excellent chemical proofing, its coating and tint permanence are undesirable.These problems that PPS exists have hindered the application of PPS to a certain extent.At present; Polyphenyl thioether composite material adopts filamentary material to carry out enhancement process mostly; Main glass (GF), carbon fine (CF) and the mineral etc. of adding, or polyphenylene sulfide (PPS) and other resin material such as polyamide (PA), polycarbonate (PC), polyester (PET) etc. are carried out blending toughening.
Ppe (PPO) is amorphous material, extraordinary dimensional stability, excellent mechanical property is arranged, surface compact; But ppe (PPO) uses separately; Exist the shortcoming of resistance to fatigue difference and stress cracking resistance difference, and its temperature resistant grade is lower than polyphenylene sulfide (PPS) below 150 ℃.
Summary of the invention
The technical problem that the present invention will solve is; Above-mentioned defective to prior art; A kind of temperature resistant grade, rigidity that can significantly not reduce polyphenylene sulfide is provided, can further improves the moulding accuracy of polyphenylene sulfide, the fiberglass enhanced polyphenyl thioether/polyphenylether composite material that also can reduce cost simultaneously.
The technical problem that the present invention further will solve is, the preparation method of the fiberglass enhanced polyphenyl thioether/polyphenylether composite material that a kind of production technique is simple, easy to operate, cost is low is provided.
The technical solution adopted for the present invention to solve the technical problems is: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process by the raw material of following parts by weight:
Polyphenylene sulfide 10.90～43.6
Ppe 10.90～43.6
Spun glass 10～55
Mineral filler 0～5
Compatilizer 1～3
Oxidation inhibitor 0～0.6
Processing aid 0.1～2.
The molecular weight of said polyphenylene sulfide is greater than 50000.
Said ppe accounts for 20～30% of raw material gross weight.
Said spun glass is the thick length of lay spun glass of alkali-free.
Said compatilizer is an ethylene-methyl acrylate copolymer.
Said mineral filler is a kind of in talcum powder, permanent white, the lime carbonate.
Said oxidation inhibitor is a kind of, two or more the mixture in phenolic antioxidant, the phosphite ester kind antioxidant.
Said phenolic antioxidant is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
Said processing aid is a kind of, two or more the mixture in lipid acid, calcium stearate, Zinic stearas, the silicone powder.
The preparation method of fiberglass enhanced polyphenyl thioether/polyphenylether composite material may further comprise the steps:
A: earlier respectively at 140～160 ℃ down and 120～140 ℃ of following forced air dryings 3～5 hours with polyphenylene sulfide, polyphenylene oxide resin;
B: take by weighing dry good polyphenylene sulfide, polyphenylene oxide resin and mineral filler, compatilizer, oxidation inhibitor, processing aid;
C: the raw material of the step b high-speed dry of putting together was mixed 4～6 minutes, obtain mixture;
D: mixture and the spun glass of step c are added twin screw extruder, melt blending, granulation;
Wherein, twin screw extruder barrel one district's temperature is 265～290 ℃, and two district's temperature are 265～300 ℃, 265～300 ℃ of three district's temperature, and 265～290 ℃ of four district's temperature, 285～300 ℃ of head temperatures stop 2～3min, pressure 12～13MPa.
The present invention adopts the mixture of polyphenylene sulfide and ppe; And through the spun glass enhancing; Be aided with mineral filler, compatilizer, oxidation inhibitor, processing aid; Obtain a kind of high performance matrix material, wherein polyphenylene sulfide and ppe make up for each other's deficiencies and learn from each other, and compare with PPO and have improved flowability, stress cracking resistance and solvent resistance; Compare with PPS, reduced cost, improved the moulding accuracy, thereby have excellent comprehensive performances.
It is compatilizer that the present invention adopts ethylene-methyl acrylate copolymer, and prepared glass strengthens the PPS/PPO matrix material and has high rigidity and toughness.Like embodiment 2 prepared composite materials, its tensile strength improves 100% than first-generation PPO matrix material, approaches spun glass and strengthens the PPS matrix material; Its bending strength ratio first-generation PPO matrix material improves 100%, approaches spun glass and strengthens the PPS matrix material, demonstrates good mechanical intensity; Its notched Izod impact strength improves 80% than pure PPS, strengthens the PPS matrix material than spun glass and improves 15%, demonstrates good impelling strength.
Matrix material resistance toheat of the present invention is good.Like embodiment 2 prepared composite materials, its thermal change type improves 50～150% than ppe first-generation matrix material, approaches spun glass and strengthens the PPS matrix material, demonstrates good heat-resistant.
The fiberglass enhanced polyphenyl thioether/polyphenylether composite material that the present invention makes has kept the good flame retardant resistance of polyphenyl thioether material.Like embodiment 2 prepared composite materials, do not adding under any situation that adds fire retardant, reach the fire-retardant rank of V0.
Preparation technology of the present invention is simple, cost is low, can obtain good economic benefit.With 60,000 yuan/ton of the market value of PPS; 30,000 yuan/ton of the market value of PPO.0.7 ten thousand yuan of/ton calculating of the market value of GF, cost of the present invention is about 30,000 yuan/ton, compares for 60,000 yuan/ton with the market value price of pure PPS, and fall is 50%.
Embodiment
Below through concrete embodiment the present invention is described.
In the matrix material raw material of the following example, oxidation inhibitor is four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Tricresyl phosphite (2,4-di-t-butyl phenyl ester) selects for use Ciba company to produce; Trade names are respectively Irganox1010, and Irganox168.Compatilizer is selected the EMA ethylene-methyl acrylate copolymer for use, produces trade names 1125AC etc. like E.I.Du Pont Company.
Embodiment 1: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process: 43.6 parts of PPS, 10.9 parts of PPO by the raw material of following parts by weight; 40 parts in the thick length of lay spun glass of alkali-free, 0.2 part of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox1010); (Irganox168) 0.2 part of tricresyl phosphite (2,4-di-t-butyl phenyl ester), 3 parts of compatilizer ethylene-methyl acrylate copolymers; 5 parts of talcum powder, 0.2 part of calcium stearate.
Preparing method: may further comprise the steps:
A: earlier respectively at 160 ℃ down and 140 ℃ of following forced air dryings 3 hours with polyphenylene sulfide, polyphenylene oxide resin;
B: take by weighing dry good polyphenylene sulfide, polyphenylene oxide resin and mineral filler, compatilizer, oxidation inhibitor, processing aid;
C: the raw material of step b put together put into the high-speed mixer high-speed dry and mixed 4 minutes, obtain mixture;
D: mixture and the spun glass of step c are added twin screw extruder, melt blending, granulation.
Among the preparation method, during melt blending, twin screw extruder barrel one district's temperature is 265 ℃, and two district's temperature are 265 ℃, 265 ℃ of three district's temperature, and 265 ℃ of four district's temperature, 285 ℃ of head temperatures stop 3min, pressure 12MPa.
Embodiment 2: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process: 32.7 parts of PPS, 21.8 parts of PPO by the raw material of following parts by weight; 40 parts in the thick length of lay spun glass of alkali-free, 0.2 part of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox1010); (Irganox168) 0.2 part of tricresyl phosphite (2,4-di-t-butyl phenyl ester), 2 parts of compatilizer ethylene-methyl acrylate copolymers; 5 parts of talcum powder, 0.2 part of Zinic stearas.
Preparing method: may further comprise the steps:
A: earlier respectively at 160 ℃ down and 140 ℃ of following forced air dryings 3 hours with polyphenylene sulfide, polyphenylene oxide resin;
B: take by weighing dry good polyphenylene sulfide, polyphenylene oxide resin and mineral filler, compatilizer, oxidation inhibitor, processing aid;
C: the raw material of step b put together put into the high-speed mixer high-speed dry and mixed 4 minutes, obtain mixture;
D: mixture and the spun glass of step c are added twin screw extruder, melt blending, granulation.
Among the preparation method, during melt blending, twin screw extruder barrel one district's temperature is 280 ℃, and two district's temperature are 280 ℃, 290 ℃ of three district's temperature, and 290 ℃ of four district's temperature, 300 ℃ of head temperatures stop 2min, pressure 13MPa.
Embodiment 3: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process: PPS21.8 part, PPO32.7 part by the raw material of following parts by weight; 40 parts in the thick length of lay spun glass of alkali-free, 0.2 part of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox1010); (Irganox168) 0.2 part of tricresyl phosphite (2,4-di-t-butyl phenyl ester), 2 parts of compatilizer ethylene-methyl acrylate copolymers; 5 parts in permanent white, 0.2 part of Zinic stearas.
Preparing method: may further comprise the steps:
A: earlier respectively at 160 ℃ down and 140 ℃ of following forced air dryings 3 hours with polyphenylene sulfide, polyphenylene oxide resin;
B: take by weighing dry good polyphenylene sulfide, polyphenylene oxide resin and mineral filler, compatilizer, oxidation inhibitor, processing aid;
C: the raw material of step b put together put into the high-speed mixer high-speed dry and mixed 4 minutes, obtain mixture;
D: mixture and the spun glass of step c are added twin screw extruder, melt blending, granulation;
Wherein, twin screw extruder barrel one district's temperature is 290 ℃, and two district's temperature are 300 ℃, 300 ℃ of three district's temperature, and 280 ℃ of four district's temperature, 280 ℃ of head temperatures stop 2.5min, pressure 12.5MPa.
Embodiment 4: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process: PPS10.9 part, PPO43.61 part by the raw material of following parts by weight; 40 parts in the thick length of lay spun glass of alkali-free, 0.2 part of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox1010); (Irganox168) 0.2 part of tricresyl phosphite (2,4-di-t-butyl phenyl ester), 1 part of compatilizer ethylene-methyl acrylate copolymer; 5 parts in permanent white, 0.2 part of Zinic stearas.
The preparation method repeats no more at this with embodiment 1.
Embodiment 5: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material, mainly process: PPS32.7 part, PPO21.8 part by the raw material of following parts by weight; 10 parts in the thick length of lay spun glass of alkali-free, 0.3 part of four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (Irganox1010); (Irganox168) 0.3 part of tricresyl phosphite (2,4-di-t-butyl phenyl ester), 1 part of compatilizer ethylene-methyl acrylate copolymer; 1 part in silicone powder, 0.2 part of Zinic stearas.
The preparation method repeats no more at this with embodiment 1.
Embodiment 6: a kind of fiberglass enhanced polyphenyl thioether/polyphenylether composite material; Mainly process: PPS21.6 part by the raw material of following parts by weight; PPO14.4 part, 55 parts in the thick length of lay spun glass of alkali-free, 2 parts of compatilizer ethylene-methyl acrylate copolymers; 2 parts in lime carbonate, 0.6 part in silicone powder, 0.1 part in lipid acid, 0.2 part of Zinic stearas.
The preparation method repeats no more at this with embodiment 1.
Performance test:
Tensile strength is tested by GB/T 1040 standards.Specimen types is the I type, batten size (mm): 170 (length) * (20 ± 0.2) (end width) * (4 ± 0.2) (thickness), and draw speed is 50mm/min;
Flexural strength and modulus in flexure are tested by GB 9341/T standard.Specimen types is specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2), rate of bending are 20mm/min;
Notched Izod impact strength is tested by GB/T 1043 standards.Specimen types is the I type, specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2); The breach type is a category-A, and the breach residual thickness is 3.2mm;
The heat-drawn wire performance is by GB GB1634 standard, and adopting heat-up rate is 130 ℃/h, and heat-transfer medium is that dimethyl silicone oil is tested.
Embodiment 1～4 raw material and material property are seen table 1:
Table 1: embodiment 1～4 raw material and material properties test be table as a result
| Form or project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PPS | 43.6 | 31.7 | 21.8 | 10.9 |
| PPO | 10.9 | 21.8 | 31.7 | 43.6 |
| GF | 40 | 40 | 40 | 40 |
| Compatilizer | 2 | 2 | 2 | 2 |
| 1010 | 0.2 | 0.2 | 0.2 | 0.2 |
| 168 | 0.2 | 0.2 | 0.2 | 0.2 |
| Processing aid | 0.2 | 0.2 | 0.2 | 0.2 |
| Notched Izod impact strength (KJ/m 2) | 10.27 | 10.73 | 10.39 | 9.25 |
| Tensile strength (MPa) | 133 | 133 | 126 | 90.67 |
| Elongation at break (%) | 10.29 | 11.06 | 12.31 | 9.53 |
| Flexural strength (MPa) | 166 | 168 | 151 | 97 |
| Modulus in flexure (MPa) | 9344 | 9520 | 8388 | 6745 |
| Thermal change type temperature (℃) | 225 | 222 | 213 | 197 |
| UL fire-retardant 1/16 | V0 | V0 | V1 | HB |
Can find out by last table, when PPO content account for gross weight in 20～30% scopes, the shock strength of spun glass enhanced PPS/PPO matrix material is very high; Intensity and modulus are all very high, and thermal change type temperature is high, and under the situation that does not add any fire retardant; Reach the fire-retardant rank of V0; With the increase of PPO content, the impact resistance of PPS/PPO matrix material descends to some extent, but all at 9.25KJ/m
2More than.From the consideration of comprehensive cost and performance, the optimum addition of PPO is about 20%.The present invention obtains the splendid fiberglass enhanced polyphenyl thioether/polyphenylether composite material of mechanical property, resistance toheat and flame retardant properties through selecting EMA as compatilizer, can satisfy the request for utilization of automobile and electrical apparatus industry.
Claims (9)
1. a fiberglass enhanced polyphenyl thioether/polyphenylether composite material is characterized in that, is mainly processed by the raw material of following parts by weight:
Wherein, said compatilizer is an ethylene-methyl acrylate copolymer.
2. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1 is characterized in that: the molecular weight of said polyphenylene sulfide is greater than 50000.
3. the preparation method of fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1 is characterized in that, said ppe accounts for 20～30% of raw material gross weight.
4. fiberglass enhanced polyphenyl thioether/polyphenylether composite material as claimed in claim 1 is characterized in that: said spun glass is the thick length of lay spun glass of alkali-free.
5. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1 is characterized in that: said mineral filler is a kind of in talcum powder, permanent white, the lime carbonate.
6. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1 is characterized in that: said oxidation inhibitor is one or more the mixture in phenolic antioxidant, the phosphite ester kind antioxidant.
7. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 6; It is characterized in that: said phenolic antioxidant is that four [3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, phosphite ester kind antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
8. fiberglass enhanced polyphenyl thioether/polyphenylether composite material according to claim 1 is characterized in that: said processing aid is one or more the mixture in lipid acid, calcium stearate, Zinic stearas, the silicone powder.
9. the preparation method of the fiberglass enhanced polyphenyl thioether/polyphenylether composite material of a claim 1 is characterized in that, may further comprise the steps:
A: earlier respectively at 140～160 ℃ down and 120～140 ℃ of following forced air dryings 3～5 hours with polyphenylene sulfide, polyphenylene oxide resin;
B: take by weighing dry good polyphenylene sulfide, polyphenylene oxide resin and mineral filler, compatilizer, oxidation inhibitor, processing aid;
C: the raw material of the step b high-speed dry of putting together was mixed 4～6 minutes, obtain mixture;
D: mixture and the spun glass of step c are added twin screw extruder, melt blending, granulation, wherein; Twin screw extruder barrel one district's temperature is 265～290 ℃, and two district's temperature are 265～300 ℃, 265～300 ℃ of three district's temperature; 265～290 ℃ of four district's temperature; 285～300 ℃ of head temperatures stop 2～3min, pressure 12～13MPa;
Wherein, in said step b, the parts by weight of said polyphenylene sulfide, polyphenylene oxide resin, mineral filler, compatilizer, oxidation inhibitor and processing aid are respectively 10.90～43.6,10.90～43.6,0～5,1～3,0～0.6 and 0.1～2; In said steps d, the parts by weight of said spun glass are 10～55.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102942790A (en) * | 2012-03-01 | 2013-02-27 | 上海真晨企业发展有限公司 | High temperature-resistant high-strength polyphenylene sulfide-based reactively reinforced and toughened composite material |
| CN103374217A (en) * | 2012-04-24 | 2013-10-30 | 苏州汉扬精密电子有限公司 | Glass fibre reinforced polyphenyl ether resin |
| CN103374216A (en) * | 2012-04-24 | 2013-10-30 | 苏州汉扬精密电子有限公司 | Glass fibre reinforced polyphenyl ether/polyphenylene sulphide composite material and preparation method for same |
| CN102643528A (en) * | 2012-05-08 | 2012-08-22 | 浙江三威防静电装备有限公司 | High-temperature anti-static polyphenyl ether composite engineering material and preparing method thereof |
| CN103509343A (en) * | 2012-06-28 | 2014-01-15 | 苏州汉扬精密电子有限公司 | Glass fiber reinforced polyphenylene sulfide/polyphenyl ether composite material and preparation method thereof |
| CN102977603B (en) * | 2012-08-23 | 2015-05-06 | 广东威林工程塑料有限公司 | High temperature resistance high heat conduction PPS/PPO alloy and preparation method thereof |
| CN102876003A (en) * | 2012-10-17 | 2013-01-16 | 余姚市富达电子有限公司 | Polyphenyl ether composite material and preparation method of polyphenyl ether composite material |
| CN103421300A (en) * | 2013-08-23 | 2013-12-04 | 苏州长盛机电有限公司 | Weather-proof enhanced PPO/PPS (polyphenylene oxide/polyphenylene sulfide) alloy and preparation method thereof |
| CN103709750B (en) * | 2013-11-28 | 2016-08-17 | 广州高八二塑料有限公司 | Mixed and modified polyphenyl thioether composite material of fibre reinforced polyphenylene oxide and preparation method thereof |
| CN103951978B (en) * | 2014-05-15 | 2016-10-26 | 成都航天精诚科技有限公司 | Polyphenylene sulfide resin composite material for aircraft head-shield and preparation method thereof |
| CN106009669B (en) * | 2016-05-25 | 2018-06-19 | 河北立格新材料科技股份有限公司 | A kind of high fire-retardance long fiber reinforced thermoplastic composites and its application |
| CN108250717A (en) * | 2016-12-29 | 2018-07-06 | 上海杰事杰新材料(集团)股份有限公司 | Composite material of the wear-resisting polyphenylene oxide of low-dielectric loss and polyphenylene sulfide and preparation method thereof |
| WO2018224314A1 (en) * | 2017-06-08 | 2018-12-13 | Solvay Specialty Polymers Usa, Llc | Polyphenylene sulfide polymer compositions and corresponding articles |
| CN107446338A (en) * | 2017-07-14 | 2017-12-08 | 广东圆融新材料有限公司 | A kind of high-glowing-filament-temperature flame-retardancy enhancing PPO/PPS composites and preparation method thereof |
| CN112708276A (en) * | 2020-12-11 | 2021-04-27 | 金发科技股份有限公司 | Polyphenylene sulfide resin composition and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135503A (en) * | 1995-03-17 | 1996-11-13 | 通用电气公司 | Polyser-poly arylidene thio-ester resin composition |
| CN1468904A (en) * | 2002-07-02 | 2004-01-21 | ͨ�õ�����˾ | Heat convertible composition containing poly (arylidene ether), its producing process and products thereby |
| CN1516723A (en) * | 2001-01-18 | 2004-07-28 | 通用电气公司 | Electrically conductive thermoset composition, method for preparation thereof and articles derived therefrom |
| CN1519275A (en) * | 2002-12-26 | 2004-08-11 | 宝理塑料株式会社 | Polyaryl sulfoether resin compsn. |
-
2008
- 2008-12-31 CN CN2008102419813A patent/CN101768359B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135503A (en) * | 1995-03-17 | 1996-11-13 | 通用电气公司 | Polyser-poly arylidene thio-ester resin composition |
| CN1516723A (en) * | 2001-01-18 | 2004-07-28 | 通用电气公司 | Electrically conductive thermoset composition, method for preparation thereof and articles derived therefrom |
| CN1468904A (en) * | 2002-07-02 | 2004-01-21 | ͨ�õ�����˾ | Heat convertible composition containing poly (arylidene ether), its producing process and products thereby |
| CN1519275A (en) * | 2002-12-26 | 2004-08-11 | 宝理塑料株式会社 | Polyaryl sulfoether resin compsn. |
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