CN116082838A - Modified polyphenylene sulfide composite material for automobile injection molding part and preparation method thereof - Google Patents
Modified polyphenylene sulfide composite material for automobile injection molding part and preparation method thereof Download PDFInfo
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- CN116082838A CN116082838A CN202211518592.7A CN202211518592A CN116082838A CN 116082838 A CN116082838 A CN 116082838A CN 202211518592 A CN202211518592 A CN 202211518592A CN 116082838 A CN116082838 A CN 116082838A
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 97
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000001746 injection moulding Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 86
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 43
- 239000003365 glass fiber Substances 0.000 claims abstract description 38
- 229910052628 phlogopite Inorganic materials 0.000 claims abstract description 38
- 239000007822 coupling agent Substances 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000000314 lubricant Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 39
- 239000004005 microsphere Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 26
- 230000003014 reinforcing effect Effects 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 abstract description 16
- 239000012752 auxiliary agent Substances 0.000 abstract description 4
- 239000011325 microbead Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 2
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- 238000005303 weighing Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- TYCLKLCKLGCVEZ-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C TYCLKLCKLGCVEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified polyphenylene sulfide composite material for an automobile injection molding part and a preparation method thereof, wherein the components comprise polyphenylene sulfide, phlogopite, hollow micro beads, calcium carbonate, long glass fiber, a phase solvent, an antioxidant, a lubricant and a coupling agent, and the phlogopite, the hollow micro beads and the calcium carbonate are firstly mixed with the coupling agent, so that a filler subjected to surface treatment is obtained; mixing the surface-treated filler, PPS and other auxiliary agents; then adding the mixed materials into a double-screw extruder for extrusion granulation, and simultaneously adding long glass fibers which are preheated and dried in advance from a glass fiber adding port of the extruder; cooling and granulating after extrusion by a double-screw extruder to obtain a polyphenylene sulfide composite material; the prepared polyphenylene sulfide composite material has the advantages of obviously improving the dimensional stability and lower linear expansion coefficient under the conditions of high strength and high wear resistance, along with simple preparation method and low manufacturing cost.
Description
Technical Field
The invention relates to the field of polymer composite materials, in particular to a modified polyphenylene sulfide composite material for an automobile injection molding part and a preparation method thereof.
Background
Polyphenylene Sulfide (PPS) is a thermoplastic resin having a phenylthio group in the molecular main chain, has excellent heat resistance, weather resistance, corrosion resistance and flame retardancy, and has been widely used as a high-strength, high-temperature-resistant thermoplastic engineering plastic in the fields of automobiles, precision instruments, electronics, machinery, aerospace and the like.
In the automotive field, PPS is mainly used for injection molding of automotive precision functional parts, such as automotive electrical systems, engine components, fuel systems, cooling systems, and heat sinks. With the rapid development of industries such as automobiles, household appliances and the like, the demand of plastic substituted steel is more remarkable, and particularly, part of automobile functional parts mainly work in extreme environments such as high temperature, high impact strength, high friction force and the like, and the performance requirement on PPS products is higher. For example, shrinkage or expansion of PPS material may affect the accuracy of automotive functions, which may create gaps, affect aesthetics, and even be dangerous. Therefore, PPS materials for the automotive field are required to have not only high strength but also high dimensional stability. In general, the smaller the coefficient of thermal expansion of a material, the better the dimensional stability of the material. At present, PPS materials have poor dimensional stability due to a large linear expansion coefficient, and it is difficult to satisfy requirements in the automotive field such as bumpers, dashboards, door panels, and the like.
At present, the prior art mainly blends polyamide polymers such as PA6 and PA66 with PPS to reduce the linear expansion coefficient of PPS. Chinese patent CN111875963a discloses a low linear expansion coefficient polyphenylene sulfide/nylon 6 composite material, which comprises the following components and raw materials in parts by weight: polyphenylene sulfide resin, nylon 6 resin, mica powder, flat glass fiber, calcium sulfate whisker, titanate coupling agent, ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzene dicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. Chinese patent CN111849164a discloses a low linear expansion coefficient polyphenylene sulfide/polyamide 66 composition, which comprises the following components in parts by weight: polyphenylene sulfide resin, polyamide 66 resin, mica powder, flat glass fiber, calcium sulfate whisker, titanate coupling agent, ethylene-maleic anhydride-glycidyl methacrylate copolymer, 2'- (1, 3-phenylene) -bisoxazoline, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 3-benzene dicarboxamide, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate. In addition, the linear expansion coefficient of the PPS composite material is also studied by adjusting auxiliary agents in the prior art. For example, chinese patent CN111073288A discloses a polyphenylene sulfide composite material with low linear expansion coefficient and a preparation method thereof, which comprises the following components and raw materials with the weight portion content: 100 parts of matrix resin, 0.1-1 part of antioxidant, 0.5-2 parts of lubricant and 30-70 parts of phlogopite.
Disclosure of Invention
The invention provides a modified polyphenylene sulfide composite material for an automobile injection molding part and a preparation method thereof, and the prepared modified polyphenylene sulfide composite material has a low linear expansion coefficient under the condition of ensuring high strength and high wear resistance, and can obviously improve the dimensional stability of the product.
In order to achieve the above purpose, the present invention provides the following technical solutions: the modified polyphenylene sulfide composite material for the automobile injection molding part and the preparation method thereof comprise the following components in parts by weight:
100 parts of polyphenylene sulfide, 30-50 parts of long glass fiber, 10-60 parts of phlogopite, 5-25 parts of hollow microsphere, 3-10 parts of calcium carbonate, 0.4-6 parts of a phase solvent, 0.3-4 parts of an antioxidant, 0.3-3 parts of a lubricant and 3-8 parts of a coupling agent.
Further, the polyphenylene sulfide is linear polyphenylene sulfide.
Further, the long glass fiber is alkali-free and untwisted glass fiber filament.
Further, the phlogopite is in the shape of a plate, a silver element, a rod or a sphere, and the particle size is 10 μm to 200 μm.
Further, the particle size of the hollow microsphere is 1250-3000 meshes.
Further, the calcium carbonate is nano-scale calcium carbonate.
Further, the phase solvent is polyolefin grafted maleic anhydride; the antioxidant is general 168; the lubricant is one or more of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, polyethylene wax, ethylene bisstearamide, ethylene-vinyl acetate copolymer or ethylene-acrylic acid copolymer; the coupling agent is selected from one of silane coupling agent KH550 or KH560 or KH 570.
The preparation method of the modified polyphenylene sulfide composite material for the automobile injection molding part comprises the following steps:
step one: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step two: then stirring the surface-treated filler, polyphenylene sulfide resin, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to be 5-30 minutes;
step three: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step four: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
The invention has the beneficial effects that:
according to the invention, the surface-treated phlogopite, the hollow microsphere, the calcium carbonate, the long glass fiber and the auxiliary agent (the cosolvent, the antioxidant and the lubricant) are simultaneously added into the polyphenylene sulfide, so that the dimensional stability of the prepared polyphenylene sulfide composite material is obviously improved under the conditions of high strength and high wear resistance, and the polyphenylene sulfide composite material has a lower linear expansion coefficient.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention;
Detailed Description
The present invention will be further described below.
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Embodiment two:
step one: weighing 100 parts of polyphenylene sulfide, 40 parts of long glass fiber, 10 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Embodiment III:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 20 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Embodiment four:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 25 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Fifth embodiment:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 15 parts of hollow microsphere, 15 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Example six:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 8 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Comparative example one:
step one: weighing 100 parts of polyphenylene sulfide, 10 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, hollow microsphere, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, and controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200 rpm;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Comparative example two:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring the hollow microspheres, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Comparative example three:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant, 1 part of a lubricant and 6 parts of a coupling agent;
step two: stirring phlogopite, calcium carbonate and a coupling agent at the temperature of 80-120 ℃ and the rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Comparative example four:
step one: weighing 100 parts of polyphenylene sulfide, 10 parts of phlogopite, 15 parts of hollow microsphere, 30 parts of long glass fiber, 1.5 parts of phase solvent, 2 parts of antioxidant, 1 part of lubricant and 6 parts of coupling agent;
step two: stirring phlogopite, hollow microsphere and coupling agent at 80-120 deg.C and 1000-2000rpm to obtain surface treated filler;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
Comparative example five:
step one: weighing 100 parts of polyphenylene sulfide, 30 parts of long glass fiber, 10 parts of phlogopite, 15 parts of hollow microsphere, 8 parts of calcium carbonate, 1.5 parts of a phase solvent, 2 parts of an antioxidant and 1 part of a lubricant;
step two: stirring phlogopite, hollow microsphere and calcium carbonate at 80-120 ℃ and rotating speed of 1000-2000rpm to obtain a filler subjected to surface treatment;
step three: stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to 5-30 minutes;
step four: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step five: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
The following is a list of the raw material compositions of examples and comparative examples (Table 1).
Table one shows the compositions of the raw materials in parts by weight of the examples and comparative examples.
The long glass fiber is not added in the first comparative example, the phlogopite is not added in the second comparative example, the hollow microsphere is not added in the third comparative example, the calcium carbonate is not added in the fourth comparative example, the coupling agent is not added in the fifth comparative example, and the long glass fiber, the phlogopite, the hollow microsphere, the calcium carbonate and the surface treatment are carried out on the phlogopite, the hollow microsphere, the calcium carbonate and the coupling agent at the same time in the examples. The extruded composite material was dried and injection molded using an injection machine to obtain standard bars.
The modified polyphenylene sulfide prepared in the above examples and comparative examples was subjected to the following performance test:
tensile strength: testing according to GB/T1040-2006 standard;
flexural strength: tested according to GB/T1843-2008 standard;
impact strength: tested according to GB/T1843-2008 standard;
relative volumetric wear: tested according to GB/T3960-1983 standard;
coefficient of linear expansion: tested according to GB/T36800.2-2018 standard;
molding shrinkage rate: tested according to GB/T15585-1995 standard;
fracture growth rate: tested according to GB/T1447-2005 standard.
The results of the performance tests are shown in Table 2, table 3.
Table 2 shows a list of properties of modified polyphenylene sulfide of examples
Table 3 shows the performance of the modified polyphenylene sulfide of comparative example
By adding the long glass fibers in the first comparative example and the first comparative example, the dimensional stability, strength, toughness and wear resistance (hardness) of the PPS composite material are obviously improved. The reason is that the long glass fiber can well enhance the bending strength of the plastic, improve the modulus of the material and reduce the shrinkage rate of the material.
By adding phlogopite in the first and the second comparative examples, the dimensional stability, strength, toughness and wear resistance (hardness) of the PPS composite material are obviously improved. The reason is that the phlogopite is used as the filler, so that the mechanical strength of the sample can be well improved, the toughness is enhanced, and the dimensional stability is enhanced.
The addition of the hollow microspheres in the first and the third comparative examples obviously improves the dimensional stability, strength, toughness and wear resistance (hardness) of the PPS composite material. The reason is that the hollow microsphere has the largest specific surface area, has large binding energy for chemical and physical binding with the matrix, and has better barrier effect on the thermal movement of the molecular chain segments.
By comparing the first and fourth examples, the addition of calcium carbonate significantly improves the dimensional stability, strength, toughness and abrasion resistance (hardness) of the PPS composite, since the addition of nano calcium carbonate has an important effect on the crystallinity of the composite. The influence of the nano calcium carbonate is mainly determined by the dispersion state of the nano calcium carbonate in the matrix and the anisotropic nucleation effect of the nano calcium carbonate.
By the addition of the coupling agent in the first and the fifth comparative examples, the phlogopite, the hollow microsphere and the calcium carbonate are subjected to surface treatment, so that the dimensional stability, the strength, the toughness and the wear resistance (hardness) of the PPS composite material are obviously improved, and the addition of the coupling agent for surface treatment can enable better compatibility between the filler and the polymer, and the dimensional stability, the strength, the toughness and the wear resistance of the submitted material.
By comparing the first and second examples, the increase in the amount of long glass fibers further improves the dimensional stability, strength, toughness and abrasion resistance (hardness) of the PPS composite.
By comparing the first and third examples, the increase in phlogopite further improves the toughness, strength and abrasion resistance of the composite.
By comparing the first embodiment with the fourth embodiment, the increase of the hollow micro beads obviously improves the dimensional stability, strength, toughness and wear resistance (hardness) of the PPS composite material.
By comparing the first and fifth examples and the fourth example, too much calcium carbonate increases the molding shrinkage of the PPS composite, because the dispersion is poor due to the large addition amount of nano calcium carbonate.
By comparing the first and sixth examples, the coupling agent of the surface-treated filler was increased, so that the dimensional stability, strength, toughness and abrasion resistance (hardness) of the PPS composite material were significantly improved.
According to the invention, the modified polyphenylene sulfide composite material with high dimensional stability, high toughness, high strength and high wear resistance can be obtained by adding the long glass fiber, the phlogopite subjected to surface treatment, the hollow microsphere, the calcium carbonate, the coupling agent and other auxiliary agents into the polyphenylene sulfide at the same time. And because the synergistic regulation and control of the component proportion and the preparation method are simpler, the manufacturing cost of the modified polyphenylene sulfide composite material provided by the invention is lower. As an injection molding material of an automobile precision functional part with high dimensional stability, the comprehensive physical properties are obviously superior to the state of the art, can completely replace the existing polyphenylene sulfide material, and has very broad market prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The foregoing embodiments are merely examples of the methods for implementing the present invention, and the descriptions thereof are more specific and detailed, and any minor modifications, equivalent substitutions and improvements made to the foregoing embodiments according to the technical principles of the present invention should be included in the protection scope of the technical solutions of the present invention.
Claims (8)
1. The modified polyphenylene sulfide composite material for the automobile injection molding part is characterized by comprising the following components in parts by weight:
100 parts of polyphenylene sulfide, 30-50 parts of long glass fiber, 10-60 parts of phlogopite, 5-25 parts of hollow microsphere, 3-10 parts of calcium carbonate, 0.4-6 parts of a phase solvent, 0.3-4 parts of an antioxidant, 0.3-3 parts of a lubricant and 3-8 parts of a coupling agent.
2. The modified polyphenylene sulfide composite for an automobile injection molded part according to claim 1, wherein the polyphenylene sulfide is a linear polyphenylene sulfide.
3. The modified polyphenylene sulfide composite material for automobile injection molding according to claim 1, wherein the long glass fiber is an alkali-free untwisted glass fiber filament.
4. The modified polyphenylene sulfide composite material for automobile injection molded parts according to claim 1, wherein the phlogopite is in the form of a plate, a silver element, a rod or a sphere, and has a particle diameter of 10 to 200. Mu.m.
5. The modified polyphenylene sulfide composite material for automobile injection molding according to claim 1, wherein the hollow microspheres have a particle size of 1250-3000 mesh.
6. The modified polyphenylene sulfide composite material for automobile injection molding according to claim 1, wherein the calcium carbonate is nano-sized calcium carbonate.
7. The modified polyphenylene sulfide composite material for automobile injection molding according to claim 1, wherein the phase solvent is polyolefin grafted maleic anhydride; the antioxidant is general 168; the lubricant is selected from one or more of silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, polyethylene wax, ethylene bisstearamide, ethylene-vinyl acetate copolymer or ethylene-acrylic acid copolymer; the coupling agent is selected from one of silane coupling agent KH550 or KH560 or KH 570.
8. The method for preparing a modified polyphenylene sulfide composite material for an automobile injection molding according to any one of claims 1 to 7, characterized by comprising the steps of:
step one: stirring phlogopite, hollow microsphere, calcium carbonate and coupling agent at 80-120deg.C and rotation speed of 1000-2000rpm to obtain surface treated filler;
step two: then stirring the surface-treated filler, polyphenylene sulfide, a phase solvent, an antioxidant and a lubricant at a rotating speed of 2000-3000rpm, heating to 70-120 ℃ to obtain a mixed material, and controlling the stirring time to be 5-30 minutes;
step three: placing the mixed material into a double-screw extruder, heating to 260-300 ℃, realizing reinforcing and toughening treatment of the material by adjusting the rotating speed, controlling the temperature of the extruder to 260-300 ℃ and the rotating speed to 800-1200rpm, and adding the preheated and dried long glass fiber;
step four: and cooling and granulating after the double-screw extruder extrudes to obtain the modified polyphenylene sulfide composite material.
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