CN112759899A - Flame-retardant high-heat-resistance resin composition and preparation method and application method thereof - Google Patents
Flame-retardant high-heat-resistance resin composition and preparation method and application method thereof Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 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 title claims abstract description 33
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 44
- 239000004417 polycarbonate Substances 0.000 claims abstract description 44
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 42
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 38
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 38
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 27
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- DBQPPCHZHNFTCV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dihydrogen phosphate Chemical compound OCCOCCOP(O)(O)=O DBQPPCHZHNFTCV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 35
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- -1 polyethylene terephthalate Polymers 0.000 claims description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229920006015 heat resistant resin Polymers 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920002857 polybutadiene Polymers 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 239000004927 clay Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001871 amorphous plastic Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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 provides a flame-retardant high-heat-resistance resin composition, a preparation method and an application method thereof, wherein the flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 60-70 parts of polycarbonate, 80-95 parts of polyethylene glycol terephthalate, 3-5.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 5.5-9 parts of modified zinc oxide coated alumina, 1.5-2.1 parts of double-spiro diethylene glycol phosphate (BDSPBP), 3-6 parts of modified multi-walled carbon nanotube, 10-15 parts of inorganic filler, 0.2-0.3 part of chain extender, 0.3-0.5 part of nucleating agent and 0.2-0.3 part of antioxidant. The resin composition prepared by the invention has strong flame retardance, good heat resistance, excellent mechanical property and wide application field.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant high-heat-resistance resin composition and a preparation method and an application method thereof.
Background
Polycarbonate (PC) is one of five general purpose engineering plastics, used in amounts second only to polyamides. Polycarbonate has high impact strength, good creep resistance, high thermal deformation temperature and excellent dimensional stability, and is widely applied to the fields of automobiles, electronic and electric appliances, machinery and the like. However, since the polycarbonate main chain contains benzene rings, the chain rigidity is high, and the melt viscosity and the fluidity are poor. When a product is injection-molded by pure polycarbonate resin, the internal stress of the material cannot be fully released, the product is easy to crack, the polycarbonate material is sensitive to the stress, and the impact strength of the polycarbonate material can be obviously reduced by impurities such as auxiliaries, toner and the like in the molding process, so that the polycarbonate and other materials are generally blended to prepare an alloy to solve the problems. Polyethylene terephthalate (PET) is an engineering plastic with excellent performance, good heat resistance, certain crystallization capacity and good solvent resistance, but the polyethylene terephthalate has a relatively high molecular chain rigidity, a high crystallization temperature and a low crystallization rate, which causes difficulty in injection molding.
Polyethylene terephthalate materials are commonly used as fiber spinning and packaging materials. However, the cost of polyethylene terephthalate is lower than that of polycarbonate and polybutylene terephthalate, so that the alloy prepared from polyethylene terephthalate and polycarbonate resin has great advantages in mechanical property, solvent resistance, excellent processability and cost. Polycarbonate is amorphous plastic, polyethylene terephthalate is crystalline plastic, generally, the compatibility of a crystalline-amorphous system is poor, but the two belong to polyester, a certain ester exchange reaction can occur in the processing process to generate a random copolymer, the compatibility of the two can be improved, and in addition, the compatibility of the two can be improved by adding different compatibilizers.
At present, most of researches on polycarbonate/polyethylene terephthalate alloys focus on the influence of a compatibilizer on material performance, and much research on flame retardancy and high heat resistance of polycarbonate/polyethylene terephthalate alloys is not carried out.
The domestic patent with the application number of CN 202010464206.5 discloses a preparation method of a flame-retardant PC-PET plastic alloy, which comprises the following steps: s1: preparing before batching, and drying the PC resin and the PET resin until the water content is less than 1%; s2: weighing the following raw materials: PC resin, PET resin, polyphosphate flame retardant, toughening agent, lubricant, antioxidant and anti-dripping agent; s3: putting the dried PC resin and PET resin, toughening agent, lubricant, antioxidant and anti-dripping agent into a stirrer, and mixing and stirring; s4: adding the stirred mixture into a double-screw extruder for melting, adding a polyphosphate flame retardant from a side feeding port of the double-screw extruder, and mixing and extruding the polyphosphate flame retardant and the melted mixture; s5: adding the extruded mixture into a spinning cooling tank for cooling; s6: and pre-drying, granulating and drying the cooled mixture. Although the plastic alloy prepared by the method has excellent performance, the flame retardance and high heat resistance of the plastic alloy can be further improved so as to meet the market requirement.
Disclosure of Invention
The invention aims to provide a flame-retardant high-heat-resistance resin composition, a preparation method and an application method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 60-70 parts of polycarbonate, 80-95 parts of polyethylene glycol terephthalate, 3-5.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 5.5-9 parts of modified zinc oxide coated alumina, 1.5-2.1 parts of double-spiro diethylene glycol phosphate (BDSPBP), 3-6 parts of modified multi-walled carbon nanotube, 10-15 parts of inorganic filler, 0.2-0.3 part of chain extender, 0.3-0.5 part of nucleating agent and 0.2-0.3 part of antioxidant.
Preferably, the polycarbonate is a bisphenol A type polycarbonate having a weight average molecular weight of 15000-20000 g/mol; the intrinsic viscosity of the polyethylene terephthalate is 0.65-0.8 dl/g.
Preferably, in the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting rate of the glycidyl methacrylate is 2-3.5%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 55-63% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
Preferably, the modified zinc oxide coated alumina is prepared by the following method:
(1) adding micron-sized alumina powder into deionized water, stirring while performing ultrasonic dispersion, then adding zinc acetate, after dissolving, keeping the temperature of the system at 40-45 ℃, slowly dropwise adding 0.1-0.2mol/L sodium hydroxide solution, after completely dropwise adding, continuing stirring while performing ultrasonic dispersion for 30-40min, then filtering, and washing with water; after washing, drying in an oven at 50-55 ℃, after drying completely, placing in an oven at 125-130 ℃, and placing for 3-5h to obtain zinc oxide coated alumina;
(2) adding water and a silane coupling agent KH550 into ethanol, heating to 50-60 ℃, uniformly stirring, adjusting the pH value to 4-5 by using dilute hydrochloric acid, then adding zinc oxide coated alumina, carrying out ultrasonic dispersion for 40-60min while stirring, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the modified zinc oxide coated alumina.
Preferably, in the step (1), the micron-sized alumina powder, zinc acetate and sodium hydroxide have a molar ratio of 10: 1: 1; the grain size of the micron-sized alumina powder is 10-50 mu m.
In the step (2), the volume ratio of the ethanol to the water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the zinc oxide coated alumina to the ethanol is 1: 5.
preferably, the modified multi-walled carbon nanotube is prepared by the following method:
(1) adding a sulfuric acid solution with the mass concentration of 70-75% into the multi-walled carbon nano-tube, heating to 50-55 ℃, stirring and ultrasonically oscillating for 3-4h, adding water for dilution, filtering, washing with water and ethanol in sequence, and then carrying out vacuum drying to obtain an acidified modified multi-walled carbon nano-tube;
(2) adding water and a silane coupling agent KH550 into ethanol, then adding the acidified modified multi-walled carbon nano-tubes, carrying out ultrasonic dispersion for 40-60min while stirring, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the modified multi-walled carbon nano-tubes.
Preferably, the volume ratio of the ethanol to the water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the acidified modified multi-walled carbon nanotube to the ethanol is 1: 3.
preferably, the inorganic filler is at least one of light calcium carbonate, diatomite and attapulgite; the chain extender is chain extender CXP 5045; the nucleating agent is a nucleating agent P250; the antioxidant is antioxidant 168 or antioxidant 1010.
The preparation method of the flame-retardant high-heat-resistance resin composition comprises the following steps: weighing the raw materials according to the proportion, drying the polycarbonate and the polyethylene terephthalate, uniformly mixing the polycarbonate, the polyethylene terephthalate and the rest raw materials in a high-speed mixer, and then placing the mixture in a double-screw extruder for extrusion, cooling and granulating to obtain the polycarbonate.
The invention has the beneficial effects that:
1. in the invention, the added silane coupling agent modified zinc oxide coated alumina has more active groups on the surface, can enhance the bonding capability with the groups of polycarbonate and polyethylene glycol terephthalate, and ensures that the modified zinc oxide coated alumina has strong dispersibility in a polymer matrix, the alumina can improve the heat resistance and the mechanical property of resin, and the zinc oxide on the surface of the alumina and the double-spiro diethylene glycol phosphate cooperate to play a good flame retardant role for the resin.
2. After the modified multi-walled carbon nanotube is modified by the sulfuric acid and the silane coupling agent, the surface functional groups of the multi-walled carbon nanotube are abundant and are stably and tightly combined with a high polymer material. The modified multi-walled carbon nanotube enhances the strength, toughness and the like of the resin on one hand, and has stronger effect on enhancing the flame retardance of the resin.
3. The added glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer can effectively enhance the compatibility between resins, and can enhance the collective performance between inorganic materials and the resins, so that the overall performance of the resin composition is enhanced. The added inorganic filler can improve the strength, toughness, heat resistance, wear resistance and the like of the material.
4. The resin composition prepared by the invention has strong flame retardance, good heat resistance, excellent mechanical property and wide application field, for example, the resin composition can be used as a material for preparing plugboards and can completely meet the national standard of the plugboard industry.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 66 parts of polycarbonate, 87 parts of polyethylene terephthalate, 4.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 8 parts of modified zinc oxide coated alumina, 1.8 parts of double-spiro diethylene glycol phosphate, 4.5 parts of modified multi-walled carbon nano tube, 13 parts of light calcium carbonate, CXP 50450.2 parts of chain extender, P2500.3 parts of nucleating agent and 1680.2 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 20000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.72 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 3%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 60% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The modified zinc oxide coated alumina is prepared by the following method:
(1) adding micron-sized alumina powder into deionized water, stirring while performing ultrasonic dispersion, then adding zinc acetate, after dissolving, keeping the temperature of the system at 45 ℃, slowly dropwise adding 0.2mol/L sodium hydroxide solution, after completely dropwise adding, continuing stirring while performing ultrasonic dispersion for 30min, then filtering, and washing with water; after washing, putting the mixture into a 55 ℃ oven for drying, putting the dried mixture into a 128 ℃ oven after drying completely, and standing for 4 hours to obtain zinc oxide coated aluminum oxide; wherein the molar ratio of the micron-sized alumina powder to the zinc acetate to the sodium hydroxide is 10: 1: 1; the micron-sized alumina powder has a particle size of 10-50 μm.
(2) Adding water and a silane coupling agent KH550 into ethanol, heating to 60 ℃, uniformly stirring, adjusting the pH value to 5 by using dilute hydrochloric acid, then adding zinc oxide coated alumina, carrying out ultrasonic dispersion for 60min while stirring, filtering, and carrying out vacuum drying at 50 ℃ to obtain the modified zinc oxide coated alumina. Wherein the volume ratio of ethanol to water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the zinc oxide coated alumina to the ethanol is 1: 5.
the modified multi-walled carbon nanotube is prepared by the following method:
(1) adding a sulfuric acid solution with the mass concentration of 75% into the multiwalled carbon nanotube, heating to 55 ℃, stirring and ultrasonically oscillating for 4 hours, adding water for dilution, filtering, washing with water and ethanol in sequence, and then carrying out vacuum drying to obtain an acidified modified multiwalled carbon nanotube;
(2) adding water and a silane coupling agent KH550 into ethanol, then adding the acidified modified multi-walled carbon nano-tubes, carrying out ultrasonic dispersion for 60min while stirring, filtering, and carrying out vacuum drying at 50 ℃ to obtain the modified multi-walled carbon nano-tubes. Wherein the volume ratio of ethanol to water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the acidified modified multi-walled carbon nanotube to the ethanol is 1: 3.
example 2:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 60 parts of polycarbonate, 85 parts of polyethylene terephthalate, 5.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 6.5 parts of modified zinc oxide coated alumina, 2.1 parts of double-spiro diethylene glycol phosphate, 4.5 parts of modified multi-walled carbon nanotubes, 13 parts of attapulgite, CXP 50450.2 parts of chain extender, P2500.3 parts of nucleating agent and 1680.3 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 20000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.8 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 3%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 60% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The modified zinc oxide coated alumina is prepared by the following method:
(1) adding micron-sized alumina powder into deionized water, stirring while performing ultrasonic dispersion, then adding zinc acetate, after dissolving, keeping the temperature of the system at 40 ℃, slowly dropwise adding 0.1mol/L sodium hydroxide solution, after completely dropwise adding, continuing stirring while performing ultrasonic dispersion for 40min, then filtering, and washing with water; after washing, drying in a 55 ℃ oven, after drying completely, placing in a 126 ℃ oven, and standing for 5h to obtain zinc oxide coated aluminum oxide; wherein the molar ratio of the micron-sized alumina powder to the zinc acetate to the sodium hydroxide is 10: 1: 1; the micron-sized alumina powder has a particle size of 10-50 μm.
(2) Adding water and a silane coupling agent KH550 into ethanol, heating to 50 ℃, uniformly stirring, adjusting the pH value to 4 by using dilute hydrochloric acid, then adding zinc oxide coated alumina, carrying out ultrasonic dispersion for 60min while stirring, filtering, and carrying out vacuum drying at 60 ℃ to obtain the modified zinc oxide coated alumina. Wherein the volume ratio of ethanol to water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the zinc oxide coated alumina to the ethanol is 1: 5.
the modified multi-walled carbon nanotube is prepared by the following method:
(1) adding a sulfuric acid solution with the mass concentration of 70% into the multi-walled carbon nano-tube, heating to 50 ℃, stirring and ultrasonically oscillating for 4 hours, adding water for dilution, filtering, washing with water and ethanol in sequence, and then carrying out vacuum drying to obtain an acidified modified multi-walled carbon nano-tube;
(2) adding water and a silane coupling agent KH550 into ethanol, then adding the acidified modified multi-walled carbon nano-tubes, carrying out ultrasonic dispersion for 40min while stirring, filtering, and carrying out vacuum drying at 60 ℃ to obtain the modified multi-walled carbon nano-tubes. Wherein the volume ratio of ethanol to water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the acidified modified multi-walled carbon nanotube to the ethanol is 1: 3.
example 3:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 65 parts of polycarbonate, 95 parts of polyethylene terephthalate, 3 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 9 parts of modified zinc oxide coated alumina, 1.5 parts of double-spiro diethylene glycol phosphate, 3 parts of modified multi-walled carbon nano tube, 10 parts of light calcium carbonate, CXP 50450.3 parts of chain extender, P2500.5 parts of nucleating agent and 10100.2 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 15000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.65 dl/g.
In the glycidyl methacrylate-grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate was 3.5%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounted for 55% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The preparation methods of the modified zinc oxide coated aluminum oxide and the modified multi-walled carbon nanotube are the same as example 1.
Example 4:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 70 parts of polycarbonate, 80 parts of polyethylene terephthalate, 4.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 5.5 parts of modified zinc oxide coated alumina, 1.6 parts of double-spiro diethylene glycol phosphate, 3.5 parts of modified multi-walled carbon nanotubes, 15 parts of diatomite, CXP 50450.2 parts of chain extender, P2500.4 parts of nucleating agent and 1680.2 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 18000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.72 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 2%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 63% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The preparation methods of the modified zinc oxide coated aluminum oxide and the modified multi-walled carbon nanotube are the same as example 2.
Example 5:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 65 parts of polycarbonate, 95 parts of polyethylene terephthalate, 4.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 6 parts of modified zinc oxide coated alumina, 2.1 parts of double-spiro diethylene glycol phosphate, 3.5 parts of modified multi-walled carbon nano tube, 10 parts of light calcium carbonate, CXP 50450.3 parts of chain extender, P2500.5 parts of nucleating agent and 1680.2 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 15000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.65 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 2%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 63% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The preparation methods of the modified zinc oxide coated aluminum oxide and the modified multi-walled carbon nanotube are the same as example 1.
Example 6:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 60 parts of polycarbonate, 90 parts of polyethylene terephthalate, 4.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 7 parts of modified zinc oxide coated alumina, 1.5 parts of double-spiro diethylene glycol phosphate, 3 parts of modified multi-walled carbon nanotubes, 15 parts of concave-convex soil, CXP 50450.3 parts of chain extender, P2500.4 parts of nucleating agent and 10100.3 parts of antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 18000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.72 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 2%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 63% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The preparation methods of the modified zinc oxide coated aluminum oxide and the modified multi-walled carbon nanotube are the same as example 2.
Example 7:
a flame-retardant high-heat-resistance resin composition comprises the following raw materials in parts by weight: 68 parts of polycarbonate, 83 parts of polyethylene terephthalate, 5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 8 parts of modified zinc oxide coated alumina, 1.8 parts of double-spiro diethylene glycol phosphate, 4.5 parts of modified multi-walled carbon nanotubes, 11 parts of attapulgite, CXP 50450.3 parts of a chain extender, P2500.5 parts of a nucleating agent and 1680.3 parts of an antioxidant.
The polycarbonate is bisphenol A polycarbonate with the weight-average molecular weight of 18000 g/mol; the intrinsic viscosity of the polyethylene terephthalate was 0.72 dl/g.
In the glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, the grafting ratio of glycidyl methacrylate is 3%, and the weight of the butadiene rubber phase in the acrylonitrile-butadiene-styrene copolymer accounts for 60% of the total weight of the acrylonitrile-butadiene-styrene copolymer.
The preparation methods of the modified zinc oxide coated aluminum oxide and the modified multi-walled carbon nanotube are the same as example 2.
The preparation method of the flame-retardant high-heat-resistance resin composition in the embodiment of the invention comprises the following steps: weighing the raw materials according to the proportion, drying the polycarbonate and the polyethylene terephthalate, uniformly mixing the polycarbonate, the polyethylene terephthalate and the rest raw materials in a high-speed mixer, and then placing the mixture in a double-screw extruder for extrusion, cooling and granulating to obtain the polycarbonate.
And (3) performance testing:
the flame-retardant and high heat-resistant resin compositions of examples 1 to 7 were subjected to a performance test.
1. Testing of tensile Property, bending Property, notched Izod impact Strength
Tensile properties were tested according to ISO 527-.
The bending properties were tested according to ISO 178-2010 with a bending rate of 2 mm/min.
The notched impact strength of the cantilever beam is tested according to ISO 180-2000, an A-type notch is selected, the notch retention width is 8mm, and the pendulum energy is 2.75J.
Table 1:
as is clear from Table 1, the resin compositions prepared in the examples of the present invention have high strength and good toughness.
2. Ball pressure test and glow wire ignition temperature test
The ball pressure test is carried out according to GB/T5169.21-2006, a standard sample plate is placed in an environment at 125 ℃, a pressure ball with the diameter of 5mm is used for applying a load of (20 +/-0.5) N, the size of the indentation diameter of the sample plate is checked after 1h, and the sample plate is regarded as passing if the diameter is smaller than 2 mm.
Glow Wire Ignition Temperature (GWIT) was tested in accordance with GB/T5169.10-2006, test temperature 770 ℃, panel thickness 3.2mm and judged as passed if there was no ignition or burning time less than 5s during application of the glow wire.
The specific performance test results are shown in table 2.
| Ball indentation diameter/mm | GWIT test (770 deg.C) | |
| Example 1 | 0.9 | By passing |
| Example 2 | 1.0 | By passing |
| Example 3 | 1.0 | By passing |
| Example 4 | 1.2 | By passing |
| Example 5 | 1.1 | By passing |
| Example 6 | 1.1 | By passing |
| Example 7 | 0.9 | By passing |
As shown in Table 2, the resin composition in the embodiment of the invention has excellent flame retardant property, the Glow Wire Ignition Temperature (GWIT) is higher than 770 ℃, and meanwhile, the resin composition can successfully pass a 125 ℃ ball pressure test, and has small ball pressure mark diameter and excellent heat resistance.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The flame-retardant high-heat-resistance resin composition is characterized by comprising the following raw materials in parts by weight: 60-70 parts of polycarbonate, 80-95 parts of polyethylene glycol terephthalate, 3-5.5 parts of glycidyl methacrylate grafted acrylonitrile-butadiene-styrene copolymer, 5.5-9 parts of modified zinc oxide coated alumina, 1.5-2.1 parts of double-spiro diethylene glycol phosphate, 3-6 parts of modified multi-walled carbon nanotube, 10-15 parts of inorganic filler, 0.2-0.3 part of chain extender, 0.3-0.5 part of nucleating agent and 0.2-0.3 part of antioxidant.
2. The flame-retardant high heat-resistant resin composition according to claim 1, wherein the polycarbonate is a bisphenol A type polycarbonate having a weight average molecular weight of 15000-20000 g/mol; the intrinsic viscosity of the polyethylene terephthalate is 0.65-0.8 dl/g.
3. The flame retardant and highly heat resistant resin composition according to claim 1, wherein the glycidyl methacrylate graft ratio of the acrylonitrile-butadiene-styrene copolymer is 2 to 3.5%, and the weight of the butadiene rubber phase of the acrylonitrile-butadiene-styrene copolymer is 55 to 63% by weight based on the total weight of the acrylonitrile-butadiene-styrene copolymer.
4. The flame-retardant high-heat-resistant resin composition according to claim 1, wherein the modified zinc oxide-coated alumina is prepared by the following method:
(1) adding micron-sized alumina powder into deionized water, stirring while performing ultrasonic dispersion, then adding zinc acetate, after dissolving, keeping the temperature of the system at 40-45 ℃, slowly dropwise adding 0.1-0.2mol/L sodium hydroxide solution, after completely dropwise adding, continuing stirring while performing ultrasonic dispersion for 30-40min, then filtering, and washing with water; after washing, drying in an oven at 50-55 ℃, after drying completely, placing in an oven at 125-130 ℃, and placing for 3-5h to obtain zinc oxide coated alumina;
(2) adding water and a silane coupling agent KH550 into ethanol, heating to 50-60 ℃, uniformly stirring, adjusting the pH value to 4-5 by using dilute hydrochloric acid, then adding zinc oxide coated alumina, carrying out ultrasonic dispersion for 40-60min while stirring, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the modified zinc oxide coated alumina.
5. The flame-retardant and high-heat-resistant resin composition according to claim 4, wherein in the step (1), the micron-sized alumina powder, the zinc acetate and the sodium hydroxide are mixed in a molar ratio of 10: 1: 1; the grain size of the micron-sized alumina powder is 10-50 mu m.
In the step (2), the volume ratio of the ethanol to the water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the zinc oxide coated alumina to the ethanol is 1: 5.
6. the flame-retardant and highly heat-resistant resin composition according to claim 1, wherein the modified multi-walled carbon nanotubes are prepared by the following method:
(1) adding a sulfuric acid solution with the mass concentration of 70-75% into the multi-walled carbon nano-tube, heating to 50-55 ℃, stirring and ultrasonically oscillating for 3-4h, adding water for dilution, filtering, washing with water and ethanol in sequence, and then carrying out vacuum drying to obtain an acidified modified multi-walled carbon nano-tube;
(2) adding water and a silane coupling agent KH550 into ethanol, then adding the acidified modified multi-walled carbon nano-tubes, carrying out ultrasonic dispersion for 40-60min while stirring, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the modified multi-walled carbon nano-tubes.
7. The flame-retardant and high-heat-resistant resin composition according to claim 6, wherein the volume ratio of the ethanol to the water to the silane coupling agent KH550 is 10: 2: 3; the mass ratio of the acidified modified multi-walled carbon nanotube to the ethanol is 1: 3.
8. the flame-retardant and highly heat-resistant resin composition according to claim 1, wherein the inorganic filler is at least one of light calcium carbonate, diatomaceous earth, attapulgite clay; the chain extender is chain extender CXP 5045; the nucleating agent is a nucleating agent P250; the antioxidant is antioxidant 168 or antioxidant 1010.
9. The method for preparing a flame-retardant high heat-resistant resin composition according to any one of claims 1 to 8, comprising the steps of: weighing the raw materials according to the proportion, drying the polycarbonate and the polyethylene terephthalate, uniformly mixing the polycarbonate, the polyethylene terephthalate and the rest raw materials in a high-speed mixer, and then placing the mixture in a double-screw extruder for extrusion, cooling and granulating to obtain the polycarbonate.
10. The method for using a flame retardant high heat resistant resin composition according to any one of claims 1 to 8, characterized in that it is used as a material for manufacturing a patch panel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558250A (en) * | 2021-12-22 | 2023-01-03 | 上海璟晏新材料有限公司 | Polyester material with high heat conductivity and water resistance and preparation method thereof |
| CN116589864A (en) * | 2023-05-22 | 2023-08-15 | 苏州博濬新材料科技有限公司 | Preparation method of heat-conductive resin composition capable of maintaining high heat conductivity |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558250A (en) * | 2021-12-22 | 2023-01-03 | 上海璟晏新材料有限公司 | Polyester material with high heat conductivity and water resistance and preparation method thereof |
| CN116589864A (en) * | 2023-05-22 | 2023-08-15 | 苏州博濬新材料科技有限公司 | Preparation method of heat-conductive resin composition capable of maintaining high heat conductivity |
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