CN115403890A - Low-floating-fiber flame-retardant polypropylene material - Google Patents
Low-floating-fiber flame-retardant polypropylene material Download PDFInfo
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- CN115403890A CN115403890A CN202211200151.2A CN202211200151A CN115403890A CN 115403890 A CN115403890 A CN 115403890A CN 202211200151 A CN202211200151 A CN 202211200151A CN 115403890 A CN115403890 A CN 115403890A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 110
- -1 polypropylene Polymers 0.000 title claims abstract description 110
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 109
- 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 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 71
- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 30
- 239000003365 glass fiber Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229920005604 random copolymer Polymers 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- CWZVMVIHYSYLSI-UHFFFAOYSA-N 1,3-dibromo-5-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfonyl-2-(2,3-dibromopropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)CBr)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 CWZVMVIHYSYLSI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229920005606 polypropylene copolymer Polymers 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 11
- 238000005452 bending Methods 0.000 abstract description 4
- 239000011152 fibreglass Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 6
- 229920006124 polyolefin elastomer Polymers 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000012661 block copolymerization Methods 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HLQNQYKRKYSHOH-UHFFFAOYSA-N [Br].[N].[P] Chemical compound [Br].[N].[P] HLQNQYKRKYSHOH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound 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 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 230000004580 weight loss Effects 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
Landscapes
- 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 low-floating-fiber flame-retardant polypropylene material which comprises the following raw materials in parts by mass: 70 to 80 parts of polypropylene resin, 2 to 6 parts of compatilizer, 1 to 5 parts of compound flame retardant, 10 to 20 parts of chopped glass fiber, 1 to 10 parts of modified filler, 0.2 to 0.8 part of compound lubricant and 0.1 to 0.5 part of antioxidant. The low-floating-fiber flame-retardant polypropylene material has UL94V-2 grade flame retardance, short flame-retardant time, good self-extinguishing property, tensile strength and bending property equivalent to those of an ABS material, and the glossiness of the low-floating-fiber flame-retardant polypropylene material reaches over 60 degrees at a test angle of 60 degrees. The low-floating-fiber glass fiber reinforced flame-retardant polypropylene material disclosed by the invention is simple in preparation method and easy to realize output, and can be applied to air conditioner bottom shells, microwave oven bases and the like instead of ABS.
Description
Technical Field
The invention belongs to the technical field of high polymer modified materials, and particularly relates to a low-floating-fiber flame-retardant polypropylene material.
Background
Polypropylene (PP) is one of five general-purpose resins, has the excellent characteristics of light weight, easiness in processing, chemical corrosion resistance and the like, and is widely applied to the industrial fields of chemical industry, electric appliances, packaging and the like. However, as the demand of polypropylene in the industries of construction, automobile, ship, and electrical and electronic insulation materials is increasing, the requirement of flame retardant property is also increasing. The polypropylene is a flammable material, the oxygen index of the polypropylene is only 17-18%, the strength is low, and the polypropylene is limited in application in household electrical products, so that the polypropylene is required to be reinforced and modified in household electrical application occasions.
The prior patent discloses a high-gloss low-floating-fiber reinforced polypropylene material for household appliances and a preparation method thereof, in particular to a high-gloss low-floating-fiber reinforced polypropylene material prepared by using atactic polypropylene, syndiotactic polypropylene, modified nano calcium carbonate, chopped glass fiber and other additives, but the calcium carbonate modification process is complex, the treatment time is long, industrialization is not easy to realize, and the calcium carbonate is added, so that the flame-retardant modification is difficult to carry out; the existing patent also discloses a polypropylene composite plastic special for electric appliances and a preparation method thereof, wherein the polypropylene is added with self-made modified short fibers and a compound flame retardant to achieve high gloss and high toughness, but the self-made modified short fibers and the compound flame retardant have complex preparation process, low production efficiency, low glass fiber addition amount and no flame retardant grade. There are also patents which improve the fluidity and the exposure of the glass fibers by adding peroxides, but this sacrifices some of the mechanical properties.
Therefore, the development of a polypropylene material with both low fiber floating and high strength flame retardant capability is a technical problem to be solved at present.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a low-floating-fiber flame-retardant polypropylene material in the first aspect, which has excellent flame-retardant property and mechanical strength, and the material has a bright surface and does not have obvious phenomenon of glass fiber exposure.
The second aspect of the invention provides a preparation method of a low-floating-fiber flame-retardant polypropylene material.
The third aspect of the invention provides an application of a low-floating-fiber flame-retardant polypropylene material.
According to the first aspect of the invention, the invention provides a low-floating-fiber flame-retardant polypropylene material, which comprises the following raw materials in parts by mass: 70 to 80 parts of polypropylene resin, 2 to 6 parts of compatilizer, 1 to 5 parts of compound flame retardant, 10 to 20 parts of chopped glass fiber, 1 to 10 parts of modified filler, 0.2 to 0.8 part of compound lubricant and 0.1 to 0.5 part of antioxidant.
In some preferred embodiments of the present invention, the low-floating-fiber flame-retardant polypropylene material comprises the following raw materials in parts by mass: 70 to 75 portions of polypropylene resin, 4 to 5 portions of compatilizer, 2 to 3 portions of compound flame retardant, 10 to 15 portions of chopped glass fiber, 5 to 10 portions of modified filler, 0.5 to 0.7 portion of compound lubricant and 0.2 to 0.4 portion of antioxidant.
In some preferred embodiments of the present invention, the polypropylene resin comprises block copolymerized polypropylene and random copolymerized polypropylene in a mass ratio of (0.5-3): 1.
In the invention, two kinds of polypropylene with different regularity are matched, and the crystallinity of the block copolymer polypropylene is influenced by the random copolymer polypropylene, thereby slowing down the setting time of the polypropylene during injection molding, wrapping more glass fibers and reducing the occurrence of fiber floating phenomenon.
In some preferred embodiments of the present invention, the melt index of the block copolymer polypropylene is 20 to 50g/10min, and more preferably 20 to 30g/10min.
In some preferred embodiments of the present invention, the notched Izod impact strength of the block copolymer polypropylene is 80J/m or more, and more preferably 120J/m or more.
The block copolymerization polypropylene is selected from at least one of block copolymerization polypropylene with the ethylene content of 7-9 percent, block copolymerization polypropylene with the ethylene content of 9-12 percent and block copolymerization polypropylene with the ethylene content of 13-15 percent.
In some preferred embodiments of the present invention, the random copolymer polypropylene has a melt index of 20g/10min or more.
In some preferred embodiments of the present invention, the random copolymer polypropylene is selected from at least one of random copolymer polypropylene having a gloss of 100 to 120 (60 °), and random copolymer polypropylene having a gloss of 120 to 140 (60 °).
In some preferred embodiments of the present invention, the compatibilizer is POE (polyolefin elastomer) grafted maleic anhydride, and the grafting ratio is 0.8% to 1.0%.
In some preferred embodiments of the present invention, the compounded lubricant comprises polyethylene wax, montanamide wax, and montanic acid ester wax in a mass ratio of (1-5): 1-3): 1.
In the invention, the compounded lubricant of polyethylene wax, montanamide wax and Montanate wax is added, so that the internal and external lubricity of the material can be improved, the dispersibility of the chopped glass fiber is improved, the surface brightness of the material is improved, and the economical efficiency is also considered.
In some preferred embodiments of the present invention, the antioxidant comprises pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1 to 2.
In some preferred embodiments of the present invention, the compounded flame retardant comprises (1-5) by mass: (10-50): (10-50): 1 octabromobisphenol S ether, aluminum hypophosphite, melamine cyanurate, and dicumyl.
In the invention, the addition amount of the flame retardant is low, free radicals are generated in the combustion process, the dripping is promoted, the flame retardant synergistic effect of bromine-phosphorus-nitrogen is exerted, and the sample strip is self-extinguished and can reach the UL94V-2 standard.
In some more preferred embodiments of the present invention, the compounded flame retardant comprises, by mass, 1.5: (30-50): (20 to 40): octabromobisphenol S ether of 1, aluminum hypophosphite, melamine cyanurate, and dicumyl chloride.
In some more preferred embodiments of the present invention, the chopped glass fibers are alkali-free chopped glass fibers, have a wire diameter of 8 to 10 μm and a length of 3 to 4mm, and have a loss on ignition at 800 ℃ of less than 0.1%.
In the invention, the selected chopped glass fiber has high purity and strength, proper length, small wire diameter and easy dispersion, and can reduce the condition of exposed glass fiber.
In some more preferred embodiments of the present invention, the modified filler is a silane coupling agent modified filler, and the filler is talc or barium sulfate; the filler is spherical or quasi-spherical, and the particle size is 2000-3000 meshes; the silane coupling agent includes but is not limited to N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N-diethyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane.
In the invention, the filler is tightly combined with the glass fiber through the polar functional group of the silane coupling agent, and the filler is used as an inorganic substance and is not easy to expose on the surface of the material in the injection molding process, so that the condition that the glass fiber is exposed can be reduced by utilizing the dragging effect of the filler, the glossiness of the surface of the material is improved, and the mechanical property and the flame retardant property of the material are not damaged.
In some more preferred embodiments of the present invention, the mass of the silane coupling agent is 0.8% to 1.0% of the mass of the filler.
According to a second aspect of the present invention, there is provided a method for preparing the low-floating-fiber flame-retardant polypropylene material according to the first aspect, comprising the following steps:
and mixing the polypropylene resin, the compatilizer, the compound flame retardant, the modified filler, the compound lubricant and the antioxidant according to the proportion, stirring, adding the chopped glass fiber, and extruding and granulating to obtain the low-floating-fiber flame-retardant polypropylene material.
In some preferred embodiments of the present invention, the method comprises the following steps:
and mixing and stirring the polypropylene resin, the compatilizer, the compound flame retardant, the modified filler, the compound lubricant and the antioxidant according to the proportion, feeding the mixture into a double-screw extruder from a main feed opening, adding the chopped glass fiber from a side feed opening, and extruding and granulating to obtain the low-floating-fiber flame-retardant polypropylene material.
In some preferred embodiments of the present invention, the method for preparing the modified filler comprises: adding the filler into a kneader, starting the kneader at 100 r/min-150 r/min, raising the temperature to 110 ℃, changing the temperature to 500 r/min-600 r/min, and stirring and drying for 5 min-8 min in an open manner to evaporate the water of the filler; adding silane coupling agent in batches, and stirring for not less than 10min to ensure that the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane fully wraps the filler; reducing the temperature to 50 ℃, discharging and packaging from a feed opening to obtain the modified filler.
In some preferred embodiments of the present invention, the twin-screw extruder has a screw diameter of 60mm to 85mm and a length to diameter ratio of 40 to 48.
In some preferred embodiments of the invention, the twin screw extruder is equipped with an automatic metering weight loss scale.
In some preferred embodiments of the present invention, the extrusion temperature of the extrusion granulation is 50 ℃ to 210 ℃.
According to a third aspect of the invention, the application of the low-floating-fiber flame-retardant polypropylene material in the preparation of electrical parts is provided.
In some embodiments of the invention, the application is to the preparation of electrical components in place of ABS materials.
In some preferred embodiments of the present invention, the electrical component is an electrical base.
In some more preferred embodiments of the present invention, the appliance is a household appliance.
The invention has the beneficial effects that:
1. the low-floating-fiber flame-retardant polypropylene material disclosed by the invention has excellent flame retardant property, the flame retardant property of the sample strips (1.5 mm and 3.0 mm) can reach UL94V-2, the flame retardant time is short, and the material has good self-extinguishing property.
2. The low-floating-fiber flame-retardant polypropylene material has tensile strength and bending property equivalent to those of ABS material, the impact strength is slightly lower than that of ABS, and the impact strength is higher than 15kJ/m 2 。
3. The surface of the low-floating-fiber flame-retardant polypropylene material disclosed by the invention has the glossiness of more than 60 under a measurement angle of 60 degrees, and is bright without obvious glass fiber exposure.
4. The low-floating-fiber flame-retardant polypropylene material disclosed by the invention selects a bromine-phosphorus-nitrogen compounded efficient flame retardant, and promotes dripping by generating free radicals in the combustion process, so that a sample strip is self-extinguished, the flame-retardant performance is stable, the addition amount of the flame retardant is low, and the cost is obviously lower than that of a bromine-antimony flame-retardant system.
5. The preparation method is relatively simple, easy to realize large-scale production, low in cost, free of using special elements, capable of combining the screws of the normal glass fiber reinforced polypropylene and stable in product quality.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the low-floating-fiber flame-retardant polypropylene material, and the specific process is as follows:
(1) Adding 100kg of talcum powder into a kneader, starting the kneader at 150r/min, heating to 110 ℃, changing the temperature to 500r/min, and stirring and baking for 5min in an open way to evaporate the water in the filler;
(2) Adding N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane in batches, and stirring for 15min to ensure that the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane fully wraps the filler;
(3) After stirring is finished, reducing the temperature to 50 ℃, discharging and packaging from a discharging opening to obtain modified talcum powder for later use;
(4) Weighing the block copolymer polypropylene EP548R (Mediterranean shell brand, MI is 28g/10min, izod impact strength is 135J/m), the random copolymer polypropylene RP348R (Mediterranean shell brand, MI is 25g/10 min), the POE grafted maleic anhydride (grafting ratio is 0.8%), the compound flame retardant (octabromobisphenol S ether: aluminum hypophosphite: melamine cyanurate: paraquat mass ratio = 1.5.
Example 2
The embodiment prepares the low-floating-fiber flame-retardant polypropylene material, and the specific process is as follows:
(1) Adding 100kg of barium sulfate into a kneader, starting the kneader at 150r/min, heating to 110 ℃, changing the temperature to 500r/min, and stirring and drying for 8min by opening a mouth to evaporate the water in the filler;
(2) Adding N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane in batches, and stirring for 15min to ensure that the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane fully wraps the filler;
(3) After stirring is finished, reducing the temperature to 50 ℃, discharging and packaging from a discharge opening to obtain modified barium sulfate for later use;
(4) Weighing the block copolymer polypropylene EP548R (Mediterranean shell brand, MI is 28g/10min, izod impact strength is 135J/m), the random copolymer polypropylene RP348R (Mediterranean shell brand, MI is 25g/10 min), POE grafted maleic anhydride (grafting ratio is 0.8%), a compound flame retardant (octabromobisphenol S ether: aluminum hypophosphite: melamine cyanurate: paraquat mass ratio = 1.5.
Comparative example 1
This comparative example prepared a polypropylene material, which differs from example 1 mainly in that no modified filler was added, the raw material ratios are shown in table 1, and the preparation process is referred to example 1.
Comparative example 2
This comparative example prepared a polypropylene material, the main difference with example 1 being the replacement of modified talc by unmodified talc, the raw material proportions are shown in table 1, the preparation process refers to example 1.
Comparative example 3
This comparative example prepared a polypropylene material, the main difference from example 2 was that the modified barium sulfate was replaced with unmodified barium sulfate, the raw material ratios are shown in table 1, and the preparation process was referred to example 2.
Comparative example 4
The comparative example prepares a polypropylene material, and the main difference from the example 1 is that the compound lubricant is replaced by polyethylene wax: ethylene bis stearamide =2:1, the proportions of the raw materials are shown in table 1, and the preparation process refers to example 1.
Comparative example 5
This comparative example prepared a polypropylene material, which differs from example 2 mainly in that no random copolymer polypropylene was added, the raw material ratios are shown in table 1, and the preparation process is referred to example 2.
Comparative example 6
This comparative example prepared a polypropylene material, the main difference from example 1 was that POE grafted maleic anhydride was replaced with PP grafted maleic anhydride, the raw material ratios are shown in table 1, and the preparation process was referred to example 1.
Comparative example 7
This comparative example prepared a polypropylene material, and the main difference from example 2 was that modified barium sulfate was replaced with modified calcium carbonate, the raw material ratio is shown in table 1, and the preparation process was referred to example 2.
Comparative example 8
The polypropylene material is prepared in the comparative example, and the main difference of the polypropylene material and the example 2 is that the compound flame retardant is octabromo bisphenol S ether: aluminum hypophosphite: melamine cyanurate: the mass ratio of the paraquat =15:10:10: the raw material ratios are shown in Table 1, and the preparation process refers to example 2.
Comparative example 9
The polypropylene material prepared by the comparative example is mainly different from the polypropylene material prepared by the example 2 in that the diameter of the chopped glass fiber is 13 microns, the length of the glass fiber is 4.5mm, the raw material proportion is shown in a table 1, and the preparation process refers to the polypropylene material prepared by the example 2.
Comparative example 10
Direct injection molding using ABS resin.
The raw material formulation of the polypropylene materials of examples 1 to 2 and comparative examples 1 to 9 is shown in table 1:
TABLE 1 raw material compounding ratio (%)
Test examples
The materials of examples 1 to 2 and comparative examples 1 to 10 were injection molded using a CG110E horizontal injection machine to obtain standard samples. The molding process conditions are as follows: injection temperature (feed inlet) 185/190/190/195 ℃ (nozzle); the injection pressure is 45MPa; the pressure maintaining time is 8s; the cooling time is 8s, the material is baked for 2h at 105 ℃ before injection molding, and the ABS resin is baked for 2h at 80 ℃. The performance tests were performed separately, with the following performance test criteria, and the results are shown in table 2:
tensile strength: testing according to ISO 527-1-2012 standard, with a thickness of 4.0mm strip;
bending property: the preparation method is carried out according to ISO 178-2019 standard, and the thickness of a sample strip is 4.0 mm;
izod notched impact performance: testing according to ISO 180-2019 standard, and obtaining a sample strip with the thickness of 4.0 mm;
and (3) flame retardant test: testing according to UL94 standard, and performing vertical combustion test on sample strips with the thickness of 1.5mm and 3.0 mm;
and (3) testing the glossiness: the test was carried out according to ISO 2813-2014 standard, and the measured gloss was recorded in the test results at 60 ° in the form of a plain square plate of 90mm by 3 mm.
Table 2 results of performance testing
As can be seen from Table 2, the low-floating-fiber flame-retardant polypropylene materials of the embodiments 1-2 of the invention have good flame retardant property and mechanical property, and 60-degree gloss is close to that of ABS resin; however, the flame-retardant polypropylene materials of comparative examples 1 to 3 have no modified filler (modified talc powder/modified barium sulfate) added thereto, or have no silane coupling agent added thereto, so that the glass fiber is not dragged by the talc powder or the barium sulfate, the glass fiber is exposed seriously, the gloss is reduced, and the surface floating is more serious than in the examples; the polypropylene material of the comparative example 4 is added with other compound lubricants, so that polar groups are lacked, the lubricating effect is poor, partial glass fibers are exposed, and the glossiness is slightly reduced; the flame-retardant polypropylene material of the comparative example 5 is the mono-additive block copolymer polypropylene, which improves the strength, but because the addition of the low-crystallinity PP is lacked, the crystallization behavior of the block copolymer polypropylene can not be well influenced, so that the PP has high cooling speed during injection molding, glass fibers can not be fully wrapped, the glossiness is seriously reduced, and the floating fibers are aggravated; the flame retardant polypropylene material of comparative example 6, in which the original POE-grafted maleic anhydride was replaced with PP-grafted maleic anhydride, resulted in an increase in tensile strength and bending properties, but a severe decrease in impact strength; the polypropylene material of comparative example 7 was prepared by adding modified calcium carbonate instead of modified barium sulfate or modified talc, but resulted in a flame retardant capability that did not achieve UL94V-2 rating; the proportion of the compound flame retardant is changed in the polypropylene material of the comparative example 8, so that the proportion of bromine, phosphorus and nitrogen in a flame retardant system is disordered, and the optimal flame retardant effect cannot be achieved; the flame-retardant polypropylene material of the comparative example 9 is changed by adding the large-wire-diameter chopped fibers, and the parameters are not in the range of the technical scheme of the application, so that the dispersibility is poor and the glossiness is reduced.
Therefore, compared with the comparative example, the low-floating-fiber flame-retardant polypropylene material provided by the technical scheme of the invention is added with the compound flame retardant in a proper proportion, matched with the compound lubricant, the modified filler and two different types of PP for use together, and then the POE graft is added, so that the flame-retardant polypropylene has excellent flame retardant property and mechanical strength, good glossiness, bright surface and no obvious exposure of glass fibers.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The low-floating-fiber flame-retardant polypropylene material is characterized by comprising the following raw materials in parts by mass: 70-80 parts of polypropylene resin, 2-6 parts of compatilizer, 1-5 parts of compound flame retardant, 10-20 parts of chopped glass fiber, 1-10 parts of modified filler, 0.2-0.8 part of compound lubricant and 0.1-0.5 part of antioxidant.
2. The low-floating-fiber flame-retardant polypropylene material according to claim 1, wherein the polypropylene resin comprises block copolymer polypropylene and random copolymer polypropylene, and the mass ratio of the block copolymer polypropylene to the random copolymer polypropylene is (0.5-3): 1.
3. The low-floating-fiber flame-retardant polypropylene material as claimed in claim 2, wherein the modified filler is a filler modified by a silane coupling agent, and the filler is talc or barium sulfate.
4. The low-floating-fiber flame-retardant polypropylene material according to claim 3, wherein the compound flame retardant comprises the following components in percentage by mass (1-5): (10-50): (10-50): 1 octabromobisphenol S ether, aluminum hypophosphite, melamine cyanurate, and dicumyl.
5. The low fiber floating flame retardant polypropylene material of claim 4, wherein the compounded lubricant comprises polyethylene wax, montanamide wax and Montanate wax in a mass ratio of (1-5): 1-3): 1.
6. The low-floating-fiber flame-retardant polypropylene material according to claim 5, wherein the chopped glass fiber is alkali-free chopped glass fiber, the wire diameter is 8-10 μm, and the length is 3-4 mm.
7. The low-floating-fiber flame-retardant polypropylene material as claimed in claim 6, wherein the compatibilizer is POE grafted maleic anhydride, and the grafting ratio is 0.8-1.0%.
8. The preparation method of the low-floating-fiber flame-retardant polypropylene material of any one of claims 1 to 7, which is characterized by comprising the following steps: and mixing the polypropylene resin, the compatilizer, the compound flame retardant, the modified filler, the compound lubricant and the antioxidant according to the proportion, stirring, adding the chopped glass fiber, and extruding and granulating to obtain the low-floating-fiber flame-retardant polypropylene material.
9. The method according to claim 8, wherein the extrusion temperature of the extrusion granulation is 50 ℃ to 210 ℃.
10. Use of the low-floating-fiber flame-retardant polypropylene material according to any one of claims 1 to 7 in the preparation of electrical parts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115851043A (en) * | 2022-12-15 | 2023-03-28 | 金发科技股份有限公司 | Spray polypropylene and preparation method and application thereof |
| CN116218080A (en) * | 2023-03-03 | 2023-06-06 | 广东聚石化学股份有限公司 | Aging-resistant flame-retardant polypropylene composite material and preparation method and application thereof |
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| CN1712445A (en) * | 2005-07-12 | 2005-12-28 | 南京航空航天大学 | Antibacterial glass fibre/nanometer particle/polypropylene composite material and production thereof |
| CN108250654A (en) * | 2018-01-18 | 2018-07-06 | 苏州银禧科技有限公司 | A kind of low floating fine fiberglass reinforced fire retardant polypropylene material |
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| CN1712445A (en) * | 2005-07-12 | 2005-12-28 | 南京航空航天大学 | Antibacterial glass fibre/nanometer particle/polypropylene composite material and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115851043A (en) * | 2022-12-15 | 2023-03-28 | 金发科技股份有限公司 | Spray polypropylene and preparation method and application thereof |
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| CN116218080A (en) * | 2023-03-03 | 2023-06-06 | 广东聚石化学股份有限公司 | Aging-resistant flame-retardant polypropylene composite material and preparation method and application thereof |
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