CN106519421A - Flame-retardant composite sheet and preparation method thereof - Google Patents
Flame-retardant composite sheet and preparation method thereof Download PDFInfo
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- CN106519421A CN106519421A CN201611068765.4A CN201611068765A CN106519421A CN 106519421 A CN106519421 A CN 106519421A CN 201611068765 A CN201611068765 A CN 201611068765A CN 106519421 A CN106519421 A CN 106519421A
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- composite sheet
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- retardant
- vinyl acetate
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- 239000002131 composite material Substances 0.000 title claims abstract description 135
- 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 115
- 239000003063 flame retardant Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 87
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 86
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 59
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 59
- 239000011256 inorganic filler Substances 0.000 claims abstract description 37
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 82
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 52
- 239000000347 magnesium hydroxide Substances 0.000 claims description 51
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 51
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 34
- 239000005543 nano-size silicon particle Substances 0.000 claims description 33
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 22
- 235000021355 Stearic acid Nutrition 0.000 claims description 17
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000008117 stearic acid Substances 0.000 claims description 17
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 16
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 15
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000007605 air drying Methods 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000012258 stirred mixture Substances 0.000 claims description 3
- 229910052567 struvite Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000011812 mixed powder Substances 0.000 description 30
- 239000000377 silicon dioxide Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- -1 polyethylene Polymers 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- HOKKHZGPKSLGJE-GSVOUGTGSA-N N-Methyl-D-aspartic acid Chemical compound CN[C@@H](C(O)=O)CC(O)=O HOKKHZGPKSLGJE-GSVOUGTGSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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 discloses a flame-retardant composite sheet. The flame-retardant composite sheet is prepared from the following raw materials: inorganic filler, a surface modifier, phosphate, a polyhydrocarbon compound, an ethylene vinyl acetate copolymer and high-density polyethylene, wherein phosphate and the polyhydrocarbon compound are taken as an intumescent flame retardant system, and the surface modifier is used for treating the surface of the inorganic filler.
Description
Technical Field
The invention belongs to the technical field of flame-retardant composite sheets, and further relates to a flame-retardant composite sheet and a preparation method thereof.
Background
With the development of scientific technology, rubber products are applied more and more, and the rubber products are used as ground mats. However, the rubber product is processed only by a mixing mode in the production process, and the production mode is single. Therefore, a rubber substitute which can use various processing modes is found, so that the industrial production level can be improved, and the production cost can be reduced. Meanwhile, the material has a flame retardant function so as to improve the use safety of the material. The ethylene-vinyl acetate copolymer (EVA) with the mass fraction of Vinyl Acetate (VA) being 18-40% has good flexibility, elasticity as rubber, good chemical stability, no toxicity, good intermingling property with filler and good coloring and forming processability.
The EVA product has a melt dripping phenomenon in the combustion process, and the EVA needs to be subjected to flame retardant modification aiming at the defects in the application. The inorganic filler can be added as a flame retardant, so that a carbon layer is formed on the surface of the composite material in the combustion process, the dripping phenomenon in the combustion process is effectively improved, the hardness of the composite material is effectively improved, and the wear resistance is improved. However, the introduction of a large amount of inorganic filler can reduce the mechanical properties of the material. Therefore, an intumescent flame retardant system is used for modification, the using amount of the inorganic flame retardant is reduced, and the mechanical property and the flame retardant property of the composite material are balanced.
High Density Polyethylene (HDPE) has strong acid and alkali resistance, organic solvent resistance, strong electrical insulation performance, good mechanical properties such as surface hardness, tensile strength, rigidity and the like, good dielectric property and environmental stress cracking resistance, and can be used as cable coatings, pipes, profiles, sheets and the like. Meanwhile, the HDPE and the EVA have good compatibility, and the resilience performance of the composite sheet can be improved by adding the HDPE.
The intumescent flame retardant is an environment-friendly flame retardant, does not contain halogen, and has the characteristic of synergistic flame retardance in the components of the system. The intumescent flame retardant comprises an acid source, a carbon source and a gas source. When heated, the carbon forming agent is dehydrated into carbon under the action of the dehydrating agent, the carbide forms a fluffy and porous carbon layer under the action of gas decomposed by the flame retardant, and the generated carbon layer can obstruct heat conduction and oxygen diffusion between the polymer and a heat source and reduce the decomposition temperature of the polymer. While also preventing the diffusion of volatile combustible gases. The intumescent flame retardant basically overcomes the defects that the halogen-containing flame retardant has large smoke generation amount and emits toxic and corrosive gases. The introduction of the intumescent flame retardant can greatly improve the threshold of material combustion.
In papers published in functional materials 2006, No. 7, 32, 1124 pages 1126 of Lihongji et al, EVA and nano SiO are prepared by a melt blending method2A composite system of particles. The experimental result shows that the nano SiO2The small size and large specific surface characteristics of the particles lend themselves to the reinforcement of toughened EVA.
Chenxi Lei et al in Chinese patent application 201310239869.7 disclose a composite inorganic flame retardant and its application in flame retardant EVA composite materials. The addition of the composite inorganic flame retardant consisting of hydroxide or magnesium salt whiskers greatly improves the oxygen index and vertical combustion performance of the EVA.
In the papers published by jiahe et al in high molecular materials science and engineering 2009, volume 25, phase 9, 109-112, ammonium polyphosphate, triazine char-forming foaming agent (CFA) and 4A molecular sieve are used as the EVA Intumescent Flame Retardant (IFR). Experiments show that when the total addition amount of IFR is 28% and the APP/CFA mass ratio is 4:1, the flame retardant EVA material has better flame retardant property.
The flame retardant property of the composite material can be obviously improved by using the flame retardant modification of the EVA, and certain effect is achieved, but the modification method of the composite material is different according to different product purposes. Aiming at the composite sheet used as a surface material, the invention uses an inorganic filler synergistic expansion flame-retardant system to carry out flame-retardant modification on an EVA matrix, and also considers the practical service performances of the composite sheet, such as the surface performance, and the like. The product can replace sheet engineering products such as rubber prepared floor mats and the like, is suitable for extrusion molding, is convenient to prepare and process, and reduces the labor intensity.
Disclosure of Invention
In view of the above, the invention aims to provide a flame-retardant composite sheet which can replace rubber to prepare sheet engineering products such as ground mats and the like, is suitable for extrusion molding, is convenient to prepare and process and reduces the labor intensity, and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the flame-retardant composite sheet comprises the following raw materials: inorganic filler, surface modifier, phosphate, multi-hydrocarbon compound, ethylene-vinyl acetate copolymer and high-density polyethylene; the phosphate and the multi-hydrocarbon compound are used as an expansion flame-retardant system, and the surface modifier is used for treating the surface of the inorganic filler;
the mass of the inorganic filler after surface modification accounts for 1-60% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 5-40% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 5-30% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 5-40%.
In a preferred embodiment of the present invention, the inorganic filler is at least one of nano titanium dioxide, nano silica, magnesium hydroxide or aluminum hydroxide.
In a preferred embodiment of the present invention, the surface modifier is at least one of sodium stearate, zinc stearate, stearic acid, a silane coupling agent, or an isocyanate coupling agent.
In a preferred embodiment of the present invention, the phosphate is at least one of ammonium polyphosphate, magnesium ammonium phosphate or phosphate.
In a preferred embodiment of the invention, the poly-hydrocarbon compound is one of starch, polyamide or pentaerythritol.
In a preferred embodiment of the invention, the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with a vinyl acetate mass fraction of 18% -40%.
The preparation method of the flame-retardant composite sheet comprises the following steps:
treating inorganic filler: mixing an inorganic filler with a prepared surface modifier solution with the mass concentration of 0.1-25% under a constant temperature condition, and then stirring; carrying out suction filtration on the stirred mixture and carrying out forced air drying to obtain the treated inorganic filler;
preparation of an intumescent flame retardant system: respectively drying the phosphate and the multi-hydrocarbon compound, and uniformly mixing according to the mass ratio of 1: 2-5: 1 to obtain an expansion flame-retardant system;
preparing a composite sheet: weighing a proper amount of ethylene-vinyl acetate copolymer and high-density polyethylene, drying, and then melting and processing the treated inorganic filler, the expansion flame-retardant system, the dried ethylene-vinyl acetate copolymer and the dried high-density polyethylene at the temperature of 90-160 ℃ to prepare the composite sheet with the thickness of 0.1-5 mm.
In a preferred embodiment of the present invention, in the step of treating the inorganic filler, the constant temperature is 40 ℃ to 90 ℃.
In a preferred embodiment of the invention, in the step of treating the inorganic filler, the inorganic filler and the prepared surface modifier solution with the mass concentration of 0.1-25% are mixed and stirred, wherein the stirring speed is 50-1500 rpm, and the stirring time is 20-80 min.
In a preferred embodiment of the present invention, in the step of preparing the composite sheet, the melt processing is performed by one of banburying/roll mixing and hot press molding or extrusion molding.
The invention has the following beneficial effects:
according to the invention, the inorganic filler is subjected to surface treatment by the surface modifier, the dispersion degree of the inorganic filler subjected to surface modification treatment in the EVA matrix and the HDPE is increased, and an expansion flame-retardant system is combined, so that the flame-retardant EVA/HDPE composite sheet has excellent flame-retardant property and anti-dripping property in the combustion process. With the addition of HDPE, the resilience of the composite sheet is obviously improved. Meanwhile, sheet-shaped engineering products such as ground mats and the like prepared by replacing rubber with EVA-based composite sheets are applied to the fields of power plants, power stations, high-speed railway carriages and the like.
Drawings
FIG. 1a is a graph comparing the tensile strength of EVA/HDPE/nano-silica composite sheets before and after the addition of nano-silica in example 1 of the present invention;
FIG. 1b is a graph showing the comparison of the elongation at break of an ethylene vinyl acetate copolymer/density polyethylene/nano-silica composite sheet before and after the addition of nano-silica in example 1 of the present invention;
FIG. 1c is a graph comparing the limiting oxygen index of ethylene vinyl acetate copolymer/density polyethylene/nano-silica composite sheets before and after the addition of nano-silica in example 1 of the present invention;
FIG. 2a is a graph comparing the tensile strength of a composite sheet of ethylene vinyl acetate/density polyethylene/titanium dioxide and nano-silica before and after the addition of nano-silica in example 2 of the present invention;
FIG. 2b is a graph comparing the elongation at break of ethylene vinyl acetate/density polyethylene/titanium dioxide and nano-silica composite sheets before and after the addition of nano-silica in example 2 of the present invention;
FIG. 2c is a graph comparing the limiting oxygen index of ethylene vinyl acetate/density polyethylene/titanium dioxide and nano-silica composite sheets before and after the addition of nano-silica in example 2 of the present invention;
FIG. 3a is a graph comparing the tensile strength of an ethylene vinyl acetate copolymer/density polyethylene/titanium dioxide composite sheet before and after the addition of nano-silica in example 3 of the present invention;
FIG. 3b is a graph comparing the elongation at break of ethylene vinyl acetate copolymer/density polyethylene/titanium dioxide composite sheets before and after the addition of nano-silica in example 3 of the present invention;
FIG. 3c is a graph comparing the limiting oxygen index of ethylene vinyl acetate copolymer/density polyethylene/titanium dioxide composite sheets before and after the addition of nano-silica in example 3 of the present invention;
FIG. 4a is a graph showing the comparison of the tensile strength of an ethylene vinyl acetate copolymer/density polyethylene/magnesium hydroxide whisker composite sheet before and after the addition of magnesium hydroxide in example 4 of the present invention;
FIG. 4b is a graph showing the comparison of the elongation at break of an ethylene vinyl acetate copolymer/density polyethylene/magnesium hydroxide whisker composite sheet before and after the addition of magnesium hydroxide in example 4 of the present invention;
FIG. 4c is a graph comparing the limiting oxygen index of ethylene vinyl acetate copolymer/density polyethylene/magnesium hydroxide whisker composite sheets before and after the addition of magnesium hydroxide in example 4 of the present invention;
FIG. 5a is a graph showing the comparison of the tensile strength of the composite sheet of the mixed powder of EVA/HDPE/ALU and MgO in example 5 before and after the mixed powder of ALUMINUM hydroxide and MgO is added;
FIG. 5b is a graph showing the comparison of the breaking elongation of the ethylene vinyl acetate/HDPE/ALUMINUM hydroxide and magnesium hydroxide mixed powder composite sheet before and after the addition of the mixed powder of aluminum hydroxide and magnesium hydroxide in example 5 of the present invention;
FIG. 5c is a graph showing the comparison of the limiting oxygen index of the ethylene vinyl acetate/HDPE/ALUMINUM hydroxide and magnesium hydroxide mixed powder composite sheet before and after the addition of the mixed powder of aluminum hydroxide and magnesium hydroxide in example 5 of the present invention;
FIG. 6a is a graph showing the comparison of the tensile strength of the composite sheet obtained from the mixed powder of EVA/HDPE/NMDA, nanosilicon dioxide, magnesium hydroxide and aluminum hydroxide before and after the addition of the mixed powder of nanosilicon dioxide, magnesium hydroxide and aluminum hydroxide in example 6 of the present invention;
FIG. 6b is a graph showing the comparison of the elongation at break of the ethylene vinyl acetate copolymer/HDPE/TIO/nanosilicon dioxide, magnesium hydroxide and aluminum hydroxide mixed powder composite sheet before and after the addition of the nanosilicon dioxide, magnesium hydroxide and aluminum hydroxide mixed powder in example 6 of the present invention;
FIG. 6c is a comparison graph of the limiting oxygen index of the ethylene vinyl acetate copolymer/density polyethylene/nano-titania, nano-silica, magnesium hydroxide and aluminum hydroxide mixed powder composite sheet before and after the nano-titania, nano-silica, magnesium hydroxide and aluminum hydroxide mixed powder is added in example 6 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
The flame-retardant composite sheet disclosed by the invention comprises the following raw materials: inorganic filler, surface modifier, phosphate, multi-hydrocarbon compound, ethylene-vinyl acetate copolymer and high-density polyethylene; the phosphate and the multi-hydrocarbon compound are used as an expansion flame-retardant system, and the surface modifier is used for treating the surface of the inorganic filler;
the mass of the inorganic filler after surface modification accounts for 1-60% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 5-40% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 5-30% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 5-40%.
Wherein the inorganic filler is at least one of nano titanium dioxide, nano silicon dioxide, magnesium hydroxide or aluminum hydroxide.
Further, the surface modifier is at least one of sodium stearate, zinc stearate, stearic acid, silane coupling agent or isocyanate coupling agent.
Further, the phosphate is at least one of ammonium polyphosphate, magnesium ammonium phosphate or phosphate.
Further, the multi-hydrocarbon compound is one of starch, polyamide or pentaerythritol.
Further, the ethylene-vinyl acetate copolymer is at least one of ethylene-vinyl acetate copolymers with the mass fraction of vinyl acetate being 18-40%.
The preparation method of the flame-retardant composite sheet comprises the following steps:
treating inorganic filler: mixing an inorganic filler with a prepared surface modifier solution with the mass concentration of 0.1-25% under a constant temperature condition, and then stirring; carrying out suction filtration on the stirred mixture and carrying out forced air drying to obtain the treated inorganic filler;
wherein the constant temperature is 40-90 ℃; the stirring conditions are that the stirring speed is 50-1500 rpm, and the stirring time is 20-80 min.
Preparation of an intumescent flame retardant system: respectively drying the phosphate and the multi-hydrocarbon compound, and uniformly mixing according to the mass ratio of 1: 2-5: 1 to obtain an expansion flame-retardant system; the temperature during expansion drying was constant 80 ℃.
Preparing a composite sheet: weighing a proper amount of ethylene-vinyl acetate copolymer and high-density polyethylene, drying, and then melting and processing the treated inorganic filler, the expansion flame-retardant system, the dried ethylene-vinyl acetate copolymer and the dried high-density polyethylene at the temperature of 90-160 ℃ to prepare the composite sheet with the thickness of 0.5-1.5 mm.
Wherein, the melting processing mode is selected from banburying/open milling and hot press molding or extrusion molding.
Example 1
(1) Surface treatment of the silane coupling agent on the nano silicon dioxide:
first, 40g of nano silica was weighed and dried. Next, a silane coupling agent solution having a concentration of 5% was prepared. And then, under the constant temperature condition of 75 ℃, carrying out surface treatment on the nano silicon dioxide by using the prepared silane coupling agent solution, and stirring for 60min at the speed of 700 rpm. The concentration of the nanosilica with respect to the silane coupling agent solution was 35%. And finally, carrying out suction filtration on the nano silicon dioxide suspension to obtain modified nano silicon dioxide, and carrying out forced air drying for later use.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electrothermal constant-temperature gulf drying oven at 80 ℃ for 4 hours, and uniformly mixing the dried ammonium polyphosphate and the pentaerythritol at room temperature to prepare the mixture with the mass ratio of 1:2 for later use.
(3) Preparation of the composite sheet:
firstly, the ethylene-vinyl acetate copolymer and the high-density polyethylene are placed in a forced air drying oven to be dried for standby. And then the mixture is melted and blended with the surface modified nano silicon dioxide and the expansion flame-retardant system in an open mill at the temperature of 125 ℃, and the mixture is hot-pressed and formed at the temperature of 140 ℃ to prepare the flame-retardant composite sheet with the thickness of 1.5 mm.
Wherein the mass of the nano silicon dioxide after surface modification accounts for 2 percent of the mass of the composite sheet. The mass of the expansion flame-retardant system accounts for 28 percent of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 30 percent of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 40 percent of the mass of the composite sheet.
Referring to FIG. 1a, FIG. 1b, FIG. 1c, wherein A is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant and nano silicon dioxide;
wherein, the dosage of the nano silicon dioxide is 2 percent, the dosage of the intumescent flame retardant system is 18 percent, and the tensile strength of the flame retardant sheet is maintained above 10 MPa. Wherein,
as can be seen from the figure, the elongation at break of the sheet is slightly improved after the inorganic nano-silica is added, which shows that the strength of the composite sheet is enhanced by the addition of the nano-silica. The limit oxygen index of the flame-retardant composite sheet reaches 28.6%, the flame-retardant grade of the flame-retardant composite sheet can reach V-0 grade, and the flame-retardant composite sheet conforms to the expected effect of the composite sheet.
Example 2
(1) Surface treatment of the mixture of sodium stearate and stearic acid on the nano titanium dioxide and the nano silicon dioxide:
first, 50g of the mixture of nano titanium dioxide and nano silicon dioxide is weighed and dried. Secondly, preparing a 12% mixed solution of sodium stearate and stearic acid. Then, under the constant temperature condition of 40 ℃, the prepared mixed solution of sodium stearate and stearic acid is used for carrying out surface treatment on the mixture of the nano titanium dioxide and the nano silicon dioxide, and the mixture is stirred for 60min at the speed of 750 rpm. The concentration of the nano titanium dioxide and nano silicon dioxide mixture relative to the mixed solution of sodium stearate and stearic acid is 40%. And finally, carrying out suction filtration on the nano titanium dioxide suspension to obtain a modified mixture of the nano titanium dioxide and the nano silicon dioxide, and carrying out air-blast drying for later use.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electrothermal constant-temperature gulf drying oven at 80 ℃ for 4 hours, and uniformly mixing the dried ammonium polyphosphate and the pentaerythritol at room temperature to prepare the mixture with the mass ratio of 1:1 for later use.
(3) Preparation of the composite sheet:
firstly, the ethylene-vinyl acetate copolymer and the high-density polyethylene are put into a forced air drying oven to be dried for standby. And then the mixture is melted and blended with the mixture of the surface modified nano titanium dioxide and the nano silicon dioxide and the expansion flame-retardant system in an internal mixer at the temperature of 140 ℃, and the mixture is hot-pressed and molded at the temperature of 150 ℃ to prepare the flame-retardant composite sheet with the thickness of 1 mm.
Wherein the mass of the nano silicon dioxide after surface modification accounts for 10% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 40% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 15% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 35% of the mass of the composite sheet.
Observing fig. 2a, fig. 2b and fig. 2c, wherein A is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant, nano titanium dioxide and nano silicon dioxide;
when the expansion flame-retardant system is added, the tensile strength of the composite sheet is reduced from 22MPa to 14.6MPa, and the elongation at break of the composite sheet is also reduced to 560%. After the nano silicon dioxide and the titanium dioxide are introduced, the tensile strength of the composite sheet is improved to 17.3MPa, and the elongation at break of the composite material is also improved. In the combustion test, the composite sheet can reach V-2 grade in UL-94 test along with the introduction of the mixture of nano titanium dioxide and nano silicon dioxide.
Example 3
(1) The surface treatment of the sodium stearate on the nano titanium dioxide comprises the following steps:
firstly, 35g of nano titanium dioxide is weighed and dried. Next, a sodium stearate solution with a concentration of 20% was prepared. Then, at the constant temperature of 90 ℃, the prepared sodium stearate solution is used for carrying out surface treatment on the nano titanium dioxide, and the stirring is carried out for 70min at the speed of 450 rpm. The concentration of nano titanium dioxide relative to the sodium stearate solution was 30%. Finally, the nano titanium dioxide suspension is filtered to obtain modified nano titanium dioxide, and is dried by air blast for later use.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electrothermal constant-temperature gulf drying oven at 80 ℃ for 4 hours, and uniformly mixing the dried ammonium polyphosphate and the pentaerythritol at room temperature to prepare the mixture with the mass ratio of 5:1 for later use.
(3) Preparation of the composite sheet:
firstly, the ethylene-vinyl acetate copolymer and the high-density polyethylene are put into a forced air drying oven to be dried for standby. And secondly, extruding and molding the ethylene-vinyl acetate copolymer, the high-density polyethylene, the flame retardant and the nano titanium dioxide on a single-screw extruder at the temperature of 130 ℃ to prepare the flame-retardant composite sheet with the thickness of 0.5 mm.
Wherein the mass of the nano titanium dioxide after surface modification accounts for 40% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 22% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 22% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 16% of the mass of the composite sheet.
Observing fig. 3a, fig. 3b and fig. 3c, wherein A is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant and nano titanium dioxide;
as can be seen from the figure, with the increase of the proportion of the flame retardant in the intumescent flame retardant system, the tensile mechanical property of the composite sheet is reduced from 26MPa to 16MPa, which is reduced by 38.5%, and the elongation at break is also reduced. After the nano titanium dioxide is introduced, the tensile mechanical property of the composite material is obviously improved. In the burn test, the composite sheet can achieve a V-1 rating in the UL-94 test.
Example 4
(1) Treatment of the surface of magnesium hydroxide whiskers with a mixture of sodium stearate, stearic acid and a silane coupling agent:
first, 40g of magnesium hydroxide whiskers are weighed and dried. Next, a mixed solution of 25% sodium stearate, stearic acid, and a silane coupling agent was prepared. Then, at the constant temperature of 60 ℃, the prepared mixed solution of sodium stearate, stearic acid and silane coupling agent is used for carrying out surface treatment on the magnesium hydroxide crystal whisker, and the stirring is carried out for 40min at the speed of 800 rpm. The concentration of magnesium hydroxide whiskers was 30% relative to the sodium stearate solution. Finally, the magnesium hydroxide whisker suspension is filtered to obtain the modified magnesium hydroxide whisker, and is dried by blast for standby.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electrothermal constant-temperature gulf drying oven at 80 ℃ for 4 hours, and uniformly mixing the dried ammonium polyphosphate and the pentaerythritol at room temperature to prepare the mixture with the mass ratio of 3:1 for later use.
(3) Preparation of the composite sheet:
firstly, the ethylene-vinyl acetate copolymer and the high-density polyethylene are put into a forced air drying oven to be dried for standby. And secondly, extruding and molding the ethylene-vinyl acetate copolymer, the high-density polyethylene, the flame retardant and the magnesium hydroxide whisker on a single-screw extruder at the temperature of 130 ℃ to prepare the flame-retardant composite sheet with the thickness of 1.5 mm.
The magnesium hydroxide whisker after surface modification accounts for 50% of the composite sheet, the expansion flame-retardant system accounts for 12% of the composite sheet, the high-density polyethylene accounts for 20% of the composite sheet, and the ethylene-vinyl acetate copolymer accounts for 18% of the composite sheet.
Observing fig. 4a, fig. 4b, fig. 4c, wherein a is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant and magnesium hydroxide whisker;
analysis shows in fig. 4 that when the amount of magnesium hydroxide is 50% and the amount of the intumescent flame retardant system is 12%, the tensile strength of the flame retardant sheet is significantly reduced compared with the sheet without the magnesium hydroxide whiskers and the intumescent flame retardant, but the tensile strength is still maintained at about 10 MPa. After the magnesium hydroxide whisker is added, the elongation at break of the sheet is improved, and the strength of the composite sheet is enhanced by adding the magnesium hydroxide whisker. The limit oxygen index of the flame-retardant composite sheet reaches 26.1%, the flame-retardant grade of the flame-retardant composite sheet can reach V-1 grade, and the flame-retardant composite sheet conforms to the expected effect of the composite sheet.
Example 5
(1) Treatment of the surface of the mixed powder of aluminum hydroxide and magnesium hydroxide by stearic acid:
first, 55g of a mixed powder of aluminum hydroxide and magnesium hydroxide was weighed and dried. Next, a silane coupling agent solution having a concentration of 10% was prepared. Then, under the condition of constant temperature of 50 ℃, the prepared stearic acid solution is used for carrying out surface treatment on the mixed powder of the aluminum hydroxide and the magnesium hydroxide, and the mixture is stirred for 25min at the speed of 1300 rpm. The concentration of the mixed powder of aluminum hydroxide and magnesium hydroxide with respect to the stearic acid solution was 15%. And finally, carrying out suction filtration on the mixed powder suspension of the aluminum hydroxide and the magnesium hydroxide to obtain modified mixed powder of the aluminum hydroxide and the magnesium hydroxide, and carrying out forced air drying for later use.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electrothermal constant-temperature gulf drying oven at 80 ℃ for 3.5 hours, and uniformly mixing the dried ammonium polyphosphate and pentaerythritol at room temperature to prepare the mixture with the mass ratio of 2:1 for later use.
(3) Preparation of the composite sheet:
firstly, putting ethylene-vinyl acetate copolymer and high-density polyethylene into an air-blowing drying oven for drying for later use, then melting and blending the ethylene-vinyl acetate copolymer and the high-density polyethylene with surface modified aluminum hydroxide and magnesium hydroxide mixed powder and an expansion flame-retardant system in an internal mixer at the temperature of 135 ℃, and carrying out hot-press forming at the temperature of 160 ℃ to prepare the flame-retardant composite sheet with the thickness of 0.8 mm.
Wherein the mass of the aluminum hydroxide and magnesium hydroxide mixed powder after surface modification accounts for 60% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 30% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 5% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 5% of the mass of the composite sheet.
Analyzing FIG. 5a, FIG. 5b, FIG. 5c, wherein A is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant, aluminum hydroxide and magnesium hydroxide;
as can be seen in fig. 5, when the intumescent flame retardant system was added, there was a significant decrease in the tensile strength of the composite sheet, and the elongation at break of the composite sheet was also reduced to 521.66%. After the mixed powder of aluminum hydroxide and magnesium hydroxide is introduced, the tensile strength of the composite sheet is improved to 13.38MPa, and the elongation at break of the composite material is increased. In the combustion test, the composite sheet can reach V-1 grade in the UL-94 test along with the introduction of the mixed powder of the aluminum hydroxide and the magnesium hydroxide.
Example 6
(1) The stearic acid is used for treating the surface of the mixed powder of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide:
firstly, 50g of mixed powder of nano titanium dioxide, nano silicon dioxide, magnesium hydroxide and aluminum hydroxide is weighed and dried. Next, a stearic acid solution having a concentration of 0.1% was prepared. Then, under the condition of constant temperature of 75 ℃, the prepared stearic acid solution is used for carrying out surface treatment on the mixed powder of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide, and the stirring is carried out for 20min at the speed of 1500 rpm. The concentration of the mixed powder of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide relative to the stearic acid solution is 20 percent. And finally, carrying out suction filtration on the modified mixed powder suspension of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide to obtain modified mixed powder of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide, and then carrying out forced air drying on the modified mixed powder of the nano titanium dioxide, the nano silicon dioxide, the magnesium hydroxide and the aluminum hydroxide for later use.
(2) Preparation of an intumescent flame retardant system:
respectively drying ammonium polyphosphate and pentaerythritol in an electric heating constant-temperature ancient air drying oven at 85 ℃ for 4 hours, and uniformly mixing the dried ammonium polyphosphate and the pentaerythritol at room temperature to prepare the mixture with the mass ratio of 3:1 for later use.
(3) Preparation of the composite sheet:
firstly, putting the ethylene-vinyl acetate copolymer and the high-density polyethylene into a forced air drying oven for drying for later use, and then extruding and molding the ethylene-vinyl acetate copolymer, the high-density polyethylene, the flame retardant and the aluminum hydroxide powder on a single-screw extruder at the temperature of 160 ℃ to prepare the flame-retardant composite sheet with the thickness of 1.2 mm.
The composite sheet material comprises a composite sheet material, wherein the mass of the surface-modified mixed powder of nano titanium dioxide, nano silicon dioxide, magnesium hydroxide and aluminum hydroxide accounts for 45% of the mass of the composite sheet material, the mass of an expansion flame-retardant system accounts for 5% of the mass of the composite sheet material, the mass of density polyethylene accounts for 25% of the mass of the composite sheet material, and the mass of ethylene-vinyl acetate copolymer accounts for 25% of the mass of the composite sheet material.
Analyzing FIG. 6a, FIG. 6b, FIG. 6c, wherein A is ethylene vinyl acetate copolymer and high density polyethylene; b is ethylene-vinyl acetate copolymer, high-density polyethylene and intumescent flame retardant; c is ethylene-vinyl acetate copolymer, high-density polyethylene, intumescent flame retardant, nano titanium dioxide, nano silicon dioxide, magnesium hydroxide and aluminum hydroxide;
as can be seen from the figure, with the increase of the proportion of the flame retardant in the intumescent flame retardant system, the tensile mechanical property of the composite sheet is reduced from 16.44MPa to 13.40MPa, which is reduced by 18.5%, and the elongation at break is also reduced. After the aluminum hydroxide powder is introduced, the tensile mechanical property of the composite material is obviously improved. In the burn test, the composite sheet can achieve a V-2 rating in the UL-94 test.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A flame-retardant composite sheet characterized by: the method comprises the following raw materials: inorganic filler, surface modifier, phosphate, multi-hydrocarbon compound, ethylene-vinyl acetate copolymer and high-density polyethylene; the phosphate and the multi-hydrocarbon compound are used as an expansion flame-retardant system, and the surface modifier is used for treating the surface of the inorganic filler;
the mass of the inorganic filler after surface modification accounts for 2-60% of the mass of the composite sheet, the mass of the expansion flame-retardant system accounts for 5-40% of the mass of the composite sheet, the mass of the high-density polyethylene accounts for 5-30% of the mass of the composite sheet, and the mass of the ethylene-vinyl acetate copolymer accounts for 5-40%.
2. The flame-retardant composite sheet according to claim 1, wherein: the inorganic filler is at least one of nano titanium dioxide, nano silicon dioxide, magnesium hydroxide or aluminum hydroxide.
3. The flame-retardant composite sheet according to claim 1, wherein: the surface modifier is at least one of sodium stearate, stearic acid or silane coupling agent.
4. The flame-retardant composite sheet according to claim 1, wherein: the phosphate is at least one of ammonium polyphosphate, magnesium ammonium phosphate or phosphate.
5. The flame-retardant composite sheet according to claim 1, wherein: the multi-hydrocarbon compound is one of starch, polyamide or pentaerythritol.
6. The flame-retardant composite sheet according to claim 1, wherein: the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer with the mass fraction of vinyl acetate being 18-40%.
7. A method for producing the flame-retardant composite sheet according to any one of claims 1 to 6, characterized by: the method comprises the following steps:
treating inorganic filler: mixing and stirring inorganic filler and a prepared surface modifier solution with the mass fraction of 0.1-25% under the constant temperature condition; carrying out suction filtration on the stirred mixture and carrying out forced air drying to obtain the treated inorganic filler;
preparation of an intumescent flame retardant system: respectively drying the phosphate and the multi-hydrocarbon compound, and uniformly mixing according to the mass ratio of 1: 2-5: 1 to obtain an expansion flame-retardant system;
preparing a composite sheet: weighing a proper amount of ethylene-vinyl acetate copolymer and high-density polyethylene, drying, and then melting and processing the treated inorganic filler, the expansion flame-retardant system, the dried ethylene-vinyl acetate copolymer and the dried high-density polyethylene at the temperature of 90-160 ℃ to prepare the composite sheet with the thickness of 0.1-5 mm.
8. The method for preparing a flame-retardant composite sheet according to claim 7, wherein: in the step of treating the inorganic filler, the constant temperature is 40-90 ℃.
9. The method for preparing a flame-retardant composite sheet according to claim 7, wherein: in the step of treating the inorganic filler, the inorganic filler and the prepared surface modifier solution with the mass concentration of 0.1-25% are mixed and stirred, wherein the stirring speed is 50-1500 rpm, and the stirring time is 20-80 min.
10. The method for preparing a flame-retardant composite sheet according to claim 7, wherein: in the preparation step of the composite sheet, the melting processing mode is one of banburying/open milling and hot press molding or extrusion molding.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003451A (en) * | 2017-12-28 | 2018-05-08 | 河南云投小镇创业孵化器有限公司 | A kind of preparation method of the environmental protection flame retardant shell of computer |
| US11237347B2 (en) | 2018-03-12 | 2022-02-01 | Corning Research & Development Corporation | Optical fiber cable with improved fire protection performance |
| CN114874532A (en) * | 2022-05-10 | 2022-08-09 | 江苏领瑞新材料科技有限公司 | High-performance optical cable thermoplastic sheath material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN101407605A (en) * | 2008-11-26 | 2009-04-15 | 东北林业大学 | Expansion flame-retardant material of polyethylene and copolymer thereof |
-
2016
- 2016-11-29 CN CN201611068765.4A patent/CN106519421A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN101407605A (en) * | 2008-11-26 | 2009-04-15 | 东北林业大学 | Expansion flame-retardant material of polyethylene and copolymer thereof |
Non-Patent Citations (3)
| Title |
|---|
| 杨中文: "《塑料用树脂及助剂》", 31 December 2009, 印刷工业出版社 * |
| 王澜等: "《高分子材料》", 31 January 2009, 中国轻工业出版社 * |
| 赵星等: "氢氧化镁对膨胀阻燃乙烯-醋酸乙烯酯共聚物性能的影响", 《塑料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003451A (en) * | 2017-12-28 | 2018-05-08 | 河南云投小镇创业孵化器有限公司 | A kind of preparation method of the environmental protection flame retardant shell of computer |
| US11237347B2 (en) | 2018-03-12 | 2022-02-01 | Corning Research & Development Corporation | Optical fiber cable with improved fire protection performance |
| US11579388B2 (en) | 2018-03-12 | 2023-02-14 | Corning Research & Development Corporation | Optical fiber cable with improved fire protection performance |
| CN114874532A (en) * | 2022-05-10 | 2022-08-09 | 江苏领瑞新材料科技有限公司 | High-performance optical cable thermoplastic sheath material and preparation method thereof |
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