CN115558204A - Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof - Google Patents
Low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN115558204A CN115558204A CN202211188368.6A CN202211188368A CN115558204A CN 115558204 A CN115558204 A CN 115558204A CN 202211188368 A CN202211188368 A CN 202211188368A CN 115558204 A CN115558204 A CN 115558204A
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- -1 polypropylene Polymers 0.000 title claims abstract description 84
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 80
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 79
- 239000003063 flame retardant Substances 0.000 title claims abstract description 55
- 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 45
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000012745 toughening agent Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000001125 extrusion Methods 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
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 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
- 239000002245 particle Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000012661 block copolymerization Methods 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 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 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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 relates to the technical field of high polymer materials, in particular to a low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and a preparation method thereof. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material comprises, by weight, 21.8-41.8% of homopolymerized polypropylene, 15% of copolymerized polypropylene, 3% of toughening agent, 2% of compatilizer, 26% of halogen-free flame retardant, 10-30% of modified whisker master batch, 0.4% of antioxidant, 0.6% of lubricant, 1-5% of hyper-dispersant and 0.2% of flame-retardant synergist. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material prepared by the invention has the characteristics of small shrinkage, good appearance effect, excellent comprehensive mechanical property and flame-retardant grade meeting UL94 vertical combustion of 1.6mmV0, and can meet the use requirements of parts used as appearance parts, requiring good dimensional stability and related product parts contacted with electronic devices.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material and a preparation method thereof.
Background
The polypropylene resin raw material has the characteristics of good comprehensive mechanical property, high heat-resistant temperature, excellent electrical insulation and excellent chemical stability to acid and alkali, wide production and processing window, low price and the like, so that the polypropylene resin raw material is widely applied to the fields of household articles, electronic appliances and the like. However, polypropylene has a low oxygen index of only about 18%, and is easy to burn, and when some elements in electronic products are locally overheated due to poor contact, overload, short circuit or other reasons, fire disasters are easily caused, so that polypropylene needs to be subjected to flame retardant modification to enable the polypropylene to have certain flame retardant performance, and because halogen-free flame retardants have small smoke during combustion, the polypropylene modified by halogen-free flame retardants is generally required to be used as a vertical combustion V0-grade flame retardant material at present; meanwhile, as some products have larger sizes or thicker glue positions, the material is required to have smaller shrinkage rate so that the final product meets the size requirement and the appearance requirement; in addition, when the product is used as an appearance member, the material is required to have a certain glossiness. Therefore, the development of a V0-grade halogen-free flame-retardant polypropylene composite material with low shrinkage and good appearance gloss is in real demand.
Chinese patent CN109721836A discloses a flame-retardant light-shielding low-shrinkage polypropylene composite material and a preparation method thereof, low shrinkage and light-shielding performance of polypropylene are endowed by adding mineral fibers, glass fibers, titanium dioxide and other auxiliaries, however, with the addition of the glass fibers, the material appearance gloss is poor, and the flame retardance can only achieve the vertical burning V2 level.
Chinese patent CN108485065A discloses a low shrinkage polypropylene material and a preparation method thereof, wherein additives such as calcium carbonate, talcum powder and magnesium hydroxide are added to endow polypropylene with low shrinkage and flame retardant property, however, the surface effect of the material is not mentioned, and because the flame retardant efficiency of the magnesium hydroxide is low, the material can only horizontally burn for less than 75mm/min in the flame retardant aspect, and can not vertically burn for V0-level flame retardant.
Chinese patent CN110964256A discloses a high-efficiency halogen-free intumescent flame-retardant glass fiber reinforced polypropylene material and a preparation method thereof, wherein the polypropylene has the characteristic of low shrinkage through the modification of glass fibers, but the surface gloss of the material is greatly influenced due to the addition of the glass fibers.
Disclosure of Invention
In order to solve the defects of low flame retardant efficiency and poor glossiness of the existing polypropylene material, the invention provides a low-shrinkage high-gloss V0-grade halogen-free flame retardant polypropylene composite material, which comprises the following raw materials in percentage by weight:
21.8 to 41.8 weight percent of homopolymerized polypropylene, 15 weight percent of copolymerized polypropylene, 3 weight percent of toughening agent, 2 weight percent of compatilizer, 26 weight percent of halogen-free flame retardant, 10 to 30 weight percent of modified whisker master batch, 0.4 weight percent of antioxidant, 0.6 weight percent of lubricant, 1 to 5 weight percent of hyperdispersant and 0.2 weight percent of flame retardant synergist.
In one embodiment, the homo-polypropylene is homo-polypropylene with high isotacticity, the isotacticity is greater than or equal to 96%, and the melt index is less than 5g/10min. Preferably, the homopolymerized polypropylene is PP501SF which is Fujian united petrochemical.
In one embodiment, the copolymerized polypropylene is medium melt-index high-resistance block copolymerized polypropylene, the melt flow rate (230 ℃ and 2.16 kg) is 5-15 g/10min, and the notch impact of the simple beam is more than 20KJ/m 2 . Preferably, the polypropylene copolymer is Lanzhou petrochemical PP SP179.
In one embodiment, the toughening agent melt flow rate (190 ℃, 2.16 kg) is greater than 20g/10min. Preferably, the toughening agent is POE8402 with high flowability of Dow USA.
In one embodiment, the compatibilizer is a photopolymerizable polypropylene grafted maleic anhydride GPM-200A.
In one embodiment, the modified whisker master batch is a self-made modified whisker master batch NP-S04-L-M61776, and the manufacturing process comprises the following steps: according to the mass ratio of (7-octen-1-yl) trimethoxy silane to deionized water of 1:3, pouring the deionized water with the temperature of 60 ℃ into a beaker filled with the (7-octen-1-yl) trimethoxy silane, standing for 1h, and standing for later use after the deionized water is hydrolyzed; adding polypropylene resin powder into a high-speed mixer heated to 80 ℃, then adding hydrolyzed (7-octen-1-yl) trimethoxysilane, and stirring at a high speed of 300r/min for 3 minutes to ensure that the hydrolyzed (7-octen-1-yl) trimethoxysilane is soaked and uniformly distributed on the surface of the polypropylene resin; then adding calcium sulfate whisker powder, and stirring at a low speed of 100r/min for 5 minutes. And then adding the mixed material into a single-screw extruder, and carrying out melting, extrusion bracing and grain cutting to obtain the modified whisker master batch NP-S04-L-M61776.
In one embodiment, the weight ratio of the polypropylene resin powder, the hydrolyzed (7-octene-1-yl) trimethoxysilane and the calcium sulfate whisker powder is (1-5): (0.01-0.1): (1-5).
In one embodiment, the calcium sulfate whisker powder has a particle length of 10-100 μm (90%), a diameter of 1-10 μm (90%), and an aspect ratio of 5-40 (90%); the purity of the (7-octen-1-yl) trimethoxy silane is more than 90 percent. Preferably, the calcium sulfate whisker powder is of Shanghai Pingguan NP-S04-L type, and the (7-octen-1-yl) trimethoxy silane is M61776 of Shanghai Mirui chemical technology Co.
In one embodiment, the antioxidant is one or more of a hindered phenolic antioxidant, a thioester antioxidant and a phosphite antioxidant.
In one embodiment, the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, ethylene bis fatty acid amide, zinc stearate, and magnesium stearate.
In one embodiment, the hyper-dispersant is Shanghai philosophy DP-1000.
In one embodiment, the flame retardant synergist is high molecular polytetrafluoroethylene coated with acrylic acid, and the molecular weight is more than or equal to 300 ten thousand. Preferably, the flame retardant synergist is Guangzhou entropy energy SN3306.
The invention also provides a preparation method of the low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material, which comprises the following steps:
(1) Weighing the homo-polypropylene, the co-polypropylene, the toughening agent, the compatilizer, the halogen-free flame retardant, the antioxidant, the lubricant, the hyper-dispersant and the flame-retardant synergist according to the weight percentage;
(2) Adding all the materials in the step (1) into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
(3) Adding the premix obtained in the step (2) into a parallel double-screw extruder from a main feeding hopper, and simultaneously adding the modified whisker master batch into the parallel double-screw extruder from a side feeding port, so that all component materials are subjected to shearing, melting, blending and extruding in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 170-190 ℃;
(4) And cooling, drying and granulating the material strips discharged from the neck mould of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material.
Based on the above, compared with the prior art, the invention has the following beneficial effects:
1. the invention improves the dispersibility of the crystal whisker in the polypropylene resin, enhances the binding force of the crystal whisker and the polypropylene resin and improves the overall performance of the composite material by a method of specially modifying the crystal whisker master batch. After hydrolysis, three methoxy genes in the molecule of the (7-octen-1-yl) trimethoxysilane are respectively replaced by hydroxyl groups to have polarity, and the surface of the inorganic filler whisker placed in the naked air also has certain polarity due to thin water layer adsorption. At this time, the hydroxyl group on the hydrolyzed (7-octen-1-yl) trimethoxysilane molecule and the water on the whisker surface are bridged by forming hydrogen bonds between molecules, and the other end of the (7-octen-1-yl) trimethoxysilane molecule is bound with the polypropylene molecular chain by physical bonding and 7-octen-1-ylmethylene long-chain molecule, so that the (7-octen-1-yl) trimethoxysilane connects the polypropylene resin and the whisker together.
2. The modified whisker master batch adopted by the invention has the function of preventing the whisker powder from agglomerating, avoids the damage of a high length-diameter ratio structure caused by strong shearing stress due to agglomeration in the subsequent double-screw blending extrusion granulation process, and keeps the reinforcing function of the whisker on the high length-diameter ratio to the polypropylene resin to the maximum extent; by coating the (7-octen-1-yl) trimethoxysilane on the crystal whisker, the (7-octen-1-yl) trimethoxysilane is used as a lubricating layer, so that the shearing force of the twin screw on the crystal whisker can be effectively weakened, the breaking probability of the crystal whisker is reduced, the high length-diameter ratio is maintained, and the good reinforcing effect on polypropylene resin is kept; the (7-octene-1-yl) trimethoxysilane is used for coating the whiskers, so that the compatibility of the whiskers and polypropylene can be increased, the bonding force of the whiskers and a polypropylene interface is improved, and the improvement of the overall mechanical property of the final composite material is facilitated.
3. The hyper-dispersant adopted by the invention is a nano-based hyper-dispersion flow improvement auxiliary agent, improves the dispersion effect of the inorganic filler in the polypropylene resin through the nano-based hyper-dispersion property, improves the melt fluidity, leads the plastic to be uniformly plasticized at a relatively low temperature, avoids appearance defects such as flow lines, pinholes, rough surface and the like, and improves the surface gloss of the plastic product.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the embodiments of the present invention with reference to the technical solutions thereof, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; 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.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
The preparation method of the modified whisker master batch NP-S04-L-M61776 comprises the following steps: (1) Pouring deionized water with the temperature of 60 ℃ into a beaker filled with (7-octen-1-yl) trimethoxysilane according to the mass ratio of (7-octen-1-yl) trimethoxysilane to the deionized water of 1:3, standing for 1h, and standing for later use after the deionized water is hydrolyzed; (2) Adding 2 parts by weight of polypropylene resin powder into a high-speed mixer heated to 80 ℃, then adding 0.02 part by weight of hydrolyzed (7-octen-1-yl) trimethoxy silane, and stirring at a high speed of 300r/min for 3 minutes to infiltrate and uniformly distribute the hydrolyzed (7-octen-1-yl) trimethoxy silane on the surface of the polypropylene resin; then adding 1 part of calcium sulfate whisker powder, and stirring at a low speed of 100r/min for 5 minutes. And then adding the mixed material into a single-screw extruder, and carrying out melting, extrusion bracing and grain cutting to obtain the modified whisker master batch NP-S04-L-M61776 for later use.
Then weighing corresponding raw materials in parts by weight in the table 1;
then, uniformly mixing the homopolymerized polypropylene, the copolymerized polypropylene, the toughening agent, the compatilizer, the halogen-free flame retardant, the antioxidant, the lubricant, the hyperdispersant and the flame retardant synergist which are weighed according to a certain proportion, adding the mixture into a parallel double-screw extruder from a main feeding port, simultaneously adding the modified whisker master batch into the parallel double-screw extruder from a side feeding port, and carrying out shearing, melting, blending and extruding on all component materials in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 170 ℃ in a first zone, 180 ℃ in a second zone, 190 ℃ in a third zone, 190 ℃ in a fourth zone, 190 ℃ in a fifth zone, 180 ℃ in a sixth zone, 180 ℃ in a seventh zone, 180 ℃ in an eighth zone, 180 ℃ in a ninth zone, 180 ℃ in a tenth zone and 190 ℃ in a machine head; and finally, cooling, drying and granulating the material strips discharged from the neck mould of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material.
TABLE 1 dosage table for each example and comparative example
Example 2
The preparation method is the same as example 1 by weighing the corresponding raw materials in parts by weight in table 1.
Example 3
The preparation method is the same as example 1 by weighing the corresponding raw materials in parts by weight in table 1.
Example 4
The preparation method is the same as example 1 by weighing the corresponding raw materials in parts by weight in table 1.
Comparative example 1
The preparation method is the same as example 1 by weighing the corresponding raw materials in parts by weight in table 1.
Comparative example 2
The preparation method is the same as that of example 1 by weighing the corresponding raw materials in parts by weight in table 1, and the experimental results are shown in table 2.
Comparative example 3
The preparation method is the same as example 1 by weighing the corresponding raw materials in parts by weight in table 1.
Comparative example 3 differs from example 4 in that comparative example 3 used a modified whisker masterbatch that was homemade NP-S04-L-CG-8830, the modified whisker masterbatch NP-S04-L-CG-8830 differing from the modified whisker masterbatch NP-S04-L-M61776 in example 4 only in that the treatment agent for NP-S04-L-M61776 was (7-octen-1-yl) trimethoxysilane M61776, and the treatment agent for NP-S04-L-CG-8830 was octyl trimethoxysilane CG-8830. The proportion of the whole components of the modified whisker master batch is unchanged.
The results obtained in the above examples and comparative examples were examined as follows: tensile strength, impact strength of a simply supported beam notch, vertical burning performance, shrinkage rate and appearance of a color plate. The specific experimental results are shown in table 2.
The specific detection methods of tensile strength, notch impact strength of the simply supported beam, vertical combustion performance and shrinkage rate are detected by referring to standards, and are not described again; the method for detecting the appearance of the color plate comprises the following steps: and (3) using a high-light color plate mold to perform injection molding on the high-light color plate, observing the surface condition of the color plate, and grading according to the following standard, wherein the higher the score is, the better the appearance condition is.
And 5, dividing: the surface of the color plate is uniform and smooth as a whole and has good luster;
and 4, dividing: the surface of the color plate is uniform and smooth as a whole, and the luster is general;
and 3, dividing: the surface of the color plate is uniform and smooth as a whole and has slight luster;
and 2, dividing: the surface of the color plate is uniform and smooth as a whole, but is rough;
1 minute: the surface of the color plate is not uniform and has obvious raised grains;
TABLE 2 Experimental results Table for each example and comparative example
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
In addition, the raw materials used may be those commercially available or prepared by methods conventional in the art, unless otherwise specified.
By combining the tables 1 and 2, it can be seen from the comparison between the examples 1 and 2 that as the proportion of the components of the modified whisker master batch NP-S04-L-M61776 is increased, the whisker has a larger length-diameter ratio, so that the shrinkage of a polypropylene molecular chain can be well inhibited, and the shrinkage of the composite material is obviously reduced; from the comparison between example 1 and example 3, it can be seen that the dispersibility of the modified whisker master batch is further improved and the gloss of the composite material becomes better as the proportion of the components of the hyperdispersant is increased; as can be seen from the comparison of comparative example 1 and example 4, the polypropylene molecular chain is not inhibited without adding the modified whisker master batch NP-S04-L-M61776, so that the composite material has large shrinkage rate due to crystallization, and the dimensional stability of the material in the actual use process is poor; from the comparison between the comparative example 2 and the example 4, the modified whisker master batch NP-S04-L-M61776 and the flame retardant have certain influence on the dispersion uniformity without adding the hyperdispersant, and further influence on the appearance effect of the composite material; from the comparison between the comparative example 3 and the example 4, octyl trimethoxy silane CG-8830 is used as a treating agent for the modified whisker master batch instead of (7-octen-1-yl) trimethoxy silane M61776, and because the end of the octyl trimethoxy silane linked with polypropylene is composed of a methylene-methyl structure, the molecular chain of the methylene-methyl structure has good flexibility and is easy to slip off when being stretched and stressed; the end of the (7-octene-1-yl) trimethoxysilane linked with the polypropylene is composed of a methylene-ethylenic bond (double bond) structure, the rigidity of the double bond structure at the tail end is relatively high, the conformation is not easy to change so as to slip from a polypropylene molecular chain when stressed, the bonding force between the whisker and the polypropylene is larger, and the mechanical property of the whole composite material is better.
In conclusion, by adopting the technical scheme of the invention, the prepared low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material has the characteristics of small shrinkage, good appearance effect, excellent comprehensive mechanical property and capability of meeting the flame-retardant level of UL94 vertical combustion of 1.6mmV0, can be used as an appearance part, has good dimensional stability, can meet the use requirements of parts of products related to contact with electronic devices, and has good industrial application value.
In addition, it will be appreciated by those skilled in the art that, although there may be many problems with the prior art, each embodiment or aspect of the present invention may be improved only in one or several respects, without necessarily simultaneously solving all the technical problems listed in the prior art or in the background. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as homo-polypropylene, co-polypropylene, toughening agent, compatibilizer, halogen-free flame retardant, modified whisker masterbatch, antioxidant, lubricant, hyperdispersant, flame retardant synergist, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention; the terms "first," "second," and the like in the description and in the claims, if any, of the embodiments of the invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material is characterized by comprising the following raw materials in percentage by weight:
21.8 to 41.8 weight percent of homopolymerized polypropylene, 15 weight percent of copolymerized polypropylene, 3 weight percent of toughening agent, 2 weight percent of compatilizer, 26 weight percent of halogen-free flame retardant, 10 to 30 weight percent of modified whisker master batch, 0.4 weight percent of antioxidant, 0.6 weight percent of lubricant, 1 to 5 weight percent of hyperdispersant and 0.2 weight percent of flame retardant synergist.
2. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, wherein: the homopolymerized polypropylene is high isotacticity homopolymerized polypropylene, the isotacticity is greater than or equal to 96%, and the melt index is less than 5g/10min.
3. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, wherein: the polypropylene copolymer isThe medium melting refers to high-resistance block copolymerization polypropylene, the melt flow rate (230 ℃, 2.16 kg) is 5-15 g/10min, the impact of a simple beam gap is more than 20KJ/M 2 。
4. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, wherein: the modified whisker master batch is a self-made modified whisker master batch NP-S04-L-M61776, and the manufacturing process comprises the following steps: pouring 60 ℃ deionized water into a beaker filled with (7-octen-1-yl) trimethoxysilane according to the mass ratio of (7-octen-1-yl) trimethoxysilane to 1:3, standing for 1h, and standing for later use after the deionized water is hydrolyzed; adding polypropylene resin powder into a high-speed mixer heated to 80 ℃, then adding hydrolyzed (7-octen-1-yl) trimethoxysilane, and stirring at a high speed of 300r/min for 3 minutes to ensure that the hydrolyzed (7-octen-1-yl) trimethoxysilane is soaked and uniformly distributed on the surface of the polypropylene resin; then adding calcium sulfate whisker powder, and stirring at a low speed of 100r/min for 5 minutes; and then adding the mixed material into a single-screw extruder, and carrying out melting, extrusion bracing and grain cutting to obtain the modified whisker master batch NP-S04-L-M61776.
5. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 4, wherein: the weight ratio of the polypropylene resin powder, the hydrolyzed (7-octene-1-yl) trimethoxysilane and the calcium sulfate whisker powder is (1-5): (0.01-0.1): (1-5).
6. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 4, wherein: the calcium sulfate whisker powder particles have the length of 10-100 mu m (90%), the diameter of 1-10 mu m (90%) and the length-diameter ratio of 5-40 (90%); the purity of the (7-octen-1-yl) trimethoxy silane is more than 90 percent.
7. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, wherein: the antioxidant is one or a combination of hindered phenol antioxidant, thioester antioxidant and phosphite antioxidant; the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, ethylene bis fatty acid amide, zinc stearate and magnesium stearate.
8. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, characterized in that: the flame-retardant synergist is macromolecular polytetrafluoroethylene coated by acrylic acid, and the molecular weight is more than or equal to 300 ten thousand.
9. The low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to claim 1, wherein: the hyper-dispersant is Shanghai philosophy DP-1000, and the compatilizer is photopolypropylene grafted maleic anhydride GPM-200A.
10. A preparation method for preparing the low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material according to any one of claims 1 to 9, which is characterized by comprising the following steps:
s100, weighing the homo-polypropylene, the co-polypropylene, the toughening agent, the compatilizer, the halogen-free flame retardant, the antioxidant, the lubricant, the hyperdispersant and the flame retardant synergist according to the weight percentage;
s200, adding all the materials obtained in the step S100 into a high-speed stirrer, and uniformly stirring and mixing at a high speed to obtain a premix;
s300, adding the premix obtained in the step S200 into a parallel double-screw extruder from a main feeding hopper, and simultaneously adding the modified whisker master batch into the parallel double-screw extruder from a side feeding port to enable all component materials to be subjected to shearing, melting, blending and extruding in the parallel double-screw extruder, wherein the processing temperature of the double-screw extruder is 170-190 ℃;
s400, cooling, drying and dicing the material strips from the neck mold of the parallel double-screw extruder to obtain the low-shrinkage high-gloss V0-grade halogen-free flame-retardant polypropylene composite material.
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