CN113061302B - Halogen-free flame-retardant long glass fiber reinforced PP composite material for bottom guard plate of automobile fuel tank - Google Patents
Halogen-free flame-retardant long glass fiber reinforced PP composite material for bottom guard plate of automobile fuel tank Download PDFInfo
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- CN113061302B CN113061302B CN202110427996.4A CN202110427996A CN113061302B CN 113061302 B CN113061302 B CN 113061302B CN 202110427996 A CN202110427996 A CN 202110427996A CN 113061302 B CN113061302 B CN 113061302B
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- halogen
- glass fiber
- free flame
- composite material
- cyclodextrin
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 80
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 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 64
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000002828 fuel tank Substances 0.000 title claims abstract description 42
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000004743 Polypropylene Substances 0.000 claims abstract description 78
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 43
- -1 polypropylene Polymers 0.000 claims abstract description 34
- 230000001681 protective effect Effects 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 14
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 238000001125 extrusion Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000806 elastomer Substances 0.000 claims description 19
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 2
- 229920003245 polyoctenamer Polymers 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- QTKVYJZLJBZISA-UHFFFAOYSA-N triethoxy(pyridin-4-yl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=NC=C1 QTKVYJZLJBZISA-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a long glass fiber reinforced PP composite material for an automobile fuel tank bottom protective plate, and particularly relates to a halogen-free flame-retardant long glass fiber reinforced PP composite material for an automobile fuel tank bottom protective plate. The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank consists of PP resin, glass fiber, a halogen-free flame retardant and an auxiliary agent, wherein the halogen-free flame retardant is a novel hydrophobic cyclodextrin-based halogen-free intumescent flame retardant prepared by combining green sustainable biomass cyclodextrin and traditional intumescent flame retardant components. The flame-retardant polypropylene composite material is simple in raw materials, reasonable in cost, excellent in flame retardant property and good in moisture barrier property, so that the increasing market demand can be met.
Description
Technical Field
The invention relates to the technical field of PP (polypropylene) composite materials, in particular to a halogen-free flame-retardant long glass fiber reinforced PP composite material for a bottom guard plate of an automobile fuel tank.
Background
In the automobile industry, the plastic replaces expensive metal materials to be the inevitable trend of development, and the high-strength engineering plastic not only reduces the processing, assembling and maintaining cost of parts, but also makes the automobile lighter, energy-saving and environment-friendly. According to the data, plastics and composite materials thereof are the most important lightweight materials for automobiles. At present, the application is particularly obvious on the bottom protection plate of the automobile fuel tank.
The glass fiber is the most widely applied reinforcement in fiber reinforced composite materials, and can be used as a reinforcement material of organic high polymers or inorganic nonmetal and composite materials. Glass fiber reinforced thermoplastic composite materials can be classified into two types, long glass fiber reinforced and short glass fiber reinforced, according to the length of the glass fiber in the matrix. Both strong and chopped glass fiber reinforced types. Compared with the short glass fiber reinforced mode, the long glass fiber reinforced thermoplastic composite material has improved strength, modulus, impact resistance, creep resistance, fatigue resistance, wear resistance, heat resistance and the like, and has great development potential in the fields of automobiles, machinery, electrical appliances, military industry and the like. However, polypropylene is an inflammable material, and after the polypropylene is compounded with glass fibers, the glass fiber reinforced polypropylene composite material is easier to burn due to the 'wick effect' of the glass fibers. Therefore, for the application of the long glass fiber reinforced polypropylene in the bottom guard plate of the fuel tank of the automobile, the flame retardant problem needs to be solved urgently, and the flame retardant difficulty is increased due to the existence of the wick effect.
In the current flame retardant market, the halogen flame retardant mainly containing bromine still has the largest output and market application share. The halogen flame retardant occupies the dominance of the flame retardant material by virtue of unique low addition amount, high efficiency and the like. However, when a fire occurs, the halogen-based flame retardant material generates a large amount of smoke, corrosive gas, and toxic dioxin, which cause secondary damage to the human body. More importantly, when the articles are discarded, particularly in landfills, the organohalogen-based flame retardants will migrate from the polymer matrix into the environment where they may form a bio-accumulation process and pose a threat to human health. The halogen-free flame retardant has the characteristics of low smoke, no release of toxic or corrosive gas and the like, overcomes the defects of halogen flame retardants, and becomes an environment-friendly flame retardant.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a halogen-free flame-retardant long glass fiber reinforced PP composite material for a bottom guard plate of an automobile fuel tank.
In order to solve the technical problems, the invention adopts the technical scheme that:
the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: PP resin, glass fiber and an auxiliary agent.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: PP resin, glass fiber, halogen-free flame retardant and auxiliary agent.
Further, the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank is composed of the following raw materials: 18-23 wt% of glass fiber, 15-24 wt% of halogen-free flame retardant, 3-7 wt% of auxiliary agent and the balance of PP resin.
The auxiliary agent is any one of polyethylene/polyoctene elastomer, polylactic acid/polyurethane elastomer and polypropylene/polystyrene elastomer.
The halogen-free flame retardant is one or more of cyclodextrin, modified cyclodextrin, melamine cyanurate, ammonium polyphosphate and magnesium hydroxide.
Generally, halogen-free intumescent flame retardants are composed primarily of three components, an acid source, a char source, and a blowing agent, and the rapid consumption of petroleum makes non-renewable petroleum-based coke sources more expensive. Under such circumstances, the exploration of new and sustainable carbon sources is receiving increasing attention due to the influence of the petroleum crisis.
The cyclodextrin is a common biomass-based material, mainly comes from starch, contains a plurality of hydroxyl groups in a molecular structure, and can be degraded to generate carbon residue with better thermal stability under inert atmosphere. Cyclodextrin is a substitute for the traditional carbon source in an intumescent flame retardant system due to the special charring capacity of cyclodextrin. And the direct blending of cyclodextrin and high molecular material can result in poor compatibility of the material and the matrix and low flame retardant efficiency.
Preferably, the halogen-free flame retardant is modified cyclodextrin.
The modified cyclodextrin is prepared by the following method:
(1) adding 18-22 parts by weight of cyclodextrin into 95-105 parts by weight of phosphoric acid, stirring for 15-30min at the rotation speed of 1000rpm of 600-;
(2) adding 17-21 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 75-85 parts by weight of melamine into 480-520 parts by weight of deionized water, stirring at 90-100 ℃ and 1500rpm for 80-100min, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at 70-90 ℃ for 10-15h to obtain pre-modified cyclodextrin;
(3) adding 13-18 parts by weight of the pre-modified cyclodextrin obtained in the step (2) and 3-8 parts by weight of a cross-linking agent into 90-110 parts by weight of absolute ethyl alcohol, then placing the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a 75-85 ℃ oven for 1.5-2.5h, centrifuging after the reaction is finished, taking bottom precipitate, washing, and drying in the 60-80 ℃ oven for 4-6h to obtain the modified cyclodextrin.
The cross-linking agent is one or more than two of polymethyl triethoxy silane, n-octyl triethoxy silane and n-octyl triethoxy silane.
Preferably, the cross-linking agent is a mixture of polymethyltriethoxysilane and 4-pyridyltriethoxysilane, and the mass ratio of the polymethyltriethoxysilane to the 4-pyridyltriethoxysilane is 3: (1-3).
According to the invention, the cyclodextrin is pre-modified by phosphoric acid and melamine, so that the particle size of the cyclodextrin is reduced, the dispersibility of the cyclodextrin in a PP matrix is improved, and part of hydroxyl on the surface of the cyclodextrin is consumed by the reaction of the phosphoric acid and the cyclodextrin, so that the hydrophilicity of the cyclodextrin is reduced.
Furthermore, after the pre-modified cyclodextrin is modified by using the cross-linking agent, unreacted hydroxyl on the surface of the cyclodextrin in the pre-modification process continuously reacts with ethoxy in the cross-linking agent, so that the modified cyclodextrin is changed from hydrophilicity to hydrophobicity along with the reduction of the number of the hydroxyl, the surface energy is greatly reduced, the compatibility and the dispersibility of the modified cyclodextrin in a PP matrix are further improved, the 'wick effect' of glass fibers is weakened, and the composite material is more compact in structure.
According to the invention, the polymethyl triethoxy silane and the 4-pyridine triethoxy silane are compounded to be used as a cross-linking agent, and firstly, both the polymethyl triethoxy silane and the 4-pyridine triethoxy silane contain ethoxy groups which can react with hydroxyl groups on cyclodextrin, so that the polarity between the cyclodextrin and a PP matrix is further reduced; and secondly, the polymethyl triethoxy silane has higher thermal degradation temperature, and the 4-pyridine triethoxy silane contains N atoms, so that the content of N elements in the modified cyclodextrin is improved. The two are used together, so that the thermal decomposition of the modified cyclodextrin can be delayed, and the thermal stability is improved.
The flame retardant mechanism analysis of the modified cyclodextrin of the invention comprises the following steps: in the first stage, the melamine structure in the modified cyclodextrin is firstly decomposed to release CO2、NH3And H2Inert gases such as O, etc., which can dilute the oxygen concentration around the combustion zone to some extent; in the second stage, the phosphoric acid structure in the modified cyclodextrin and the cyclodextrin structure are subjected to thermal esterification reaction to generate carbon residue with a cross-linking structure (P-O-P and P-O-C groups); in the third stage, under the induction action of inert gas, the carbon slag gradually forms compact, expanded and continuous carbon with a graphitized structureThe strong blocking effect of the carbon layer can effectively inhibit heat and mass transfer between the combustion area and the composite material matrix, and further the flame retardant property of the modified cyclodextrin is realized.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying the PP resin, the glass fiber, the halogen-free flame retardant and the auxiliary agent for 10-15h at 65-75 ℃, then weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 5-15min at the rotation speed of 400-600rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, drying at the temperature of 75-85 ℃ for 10-15 hours, and obtaining the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the rotation speed of the screw is 150-300rpm, and the working temperature of the extrusion section is 120-210 ℃.
The invention has the following technical effects:
1. according to the invention, the green sustainable biomass cyclodextrin and the traditional intumescent flame retardant component are combined to prepare the novel hydrophobic cyclodextrin-based halogen-free intumescent flame retardant, the surface hydrophilicity of the cyclodextrin is converted into the hydrophobicity, the compatibility and the dispersibility between the cyclodextrin material and the PP matrix are greatly improved, and the improvement of the flame retardant efficiency is further promoted.
2. The single component integral structures used in the present invention are more viable for dispersion in PP matrices than are multi-component systems.
3. The modified cyclodextrin disclosed by the invention is small in particle size, and after the modified cyclodextrin is modified by a cross-linking agent, the compatibility between glass fibers and a PP matrix is improved, so that the 'wick effect' of the glass fibers is weakened, the structure of a composite material is more compact, the flame retardant property can be improved, and the moisture barrier property can be improved.
4. The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank has the advantages of simple raw materials, reasonable cost, excellent flame retardant property and good moisture barrier property, thereby meeting the increasing market demand.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
polyethylene polyoctene elastomer, brand Spanish Dow, designation DE2300, density 1.16g/cm3Purchased from Ruisheng plastics Co., Ltd, of Foshan City.
PP resin, CAS No.: 9003-07-0, trade name: L5E89, available from Petroleum gas, Inc., China.
Glass fiber, CAS No.: 65997-17-3, short glass fiber filament, available from QIANVIXIN MATERIALS GmbH, Leshan.
Cyclodextrins, the present invention uses β -cyclodextrin, CAS No.: 7585-39-9, available from Zhengzhou Kangyuan chemical products Co.
Phosphoric acid, CAS No.: 7664-38-2, purity: 85% of the total weight.
Melamine, CAS No.: 108-78-1, available from Shanghai Michelin Biotechnology, Inc.
Polymethyl triethoxy silane, density: 1.0g/cm3The model is as follows: yn-303, available from Shandong dao Sheng chemical science and technology Co.
4-pyridyltriethoxysilane, CAS No.: 166262-04-0, which is purchased from Shanghai Qingliu chemical science and technology center.
Example 1
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 75 wt% PP resin, 20 wt% glass fiber and 5 wt% polyethylene polyoctene elastomer.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying the PP resin, the glass fiber and the polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at a rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Example 2
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% PP resin, 20 wt% glass fiber, 20 wt% cyclodextrin and 5 wt% polyethylene polyoctene elastomer.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying PP resin, glass fiber, cyclodextrin and polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at the rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Comparative example 1
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% PP resin, 20 wt% glass fiber, 20 wt% melamine and 5 wt% polyethylene polyoctene elastomer.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying PP resin, glass fiber, melamine and polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at a rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Example 3
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% of PP resin, 20 wt% of glass fiber, 20 wt% of pre-modified cyclodextrin and 5 wt% of polyethylene polyoctene elastomer.
The pre-modified cyclodextrin is prepared by the following method:
(1) adding 20 parts by weight of cyclodextrin into 100 parts by weight of phosphoric acid, stirring at the rotating speed of 800rpm for 20min, then placing into a reaction kettle with a polytetrafluoroethylene lining, placing into a drying oven at 100 ℃ for keeping for 1h, centrifuging after the reaction is finished, taking a bottom precipitate, washing, and drying in the drying oven at 60 ℃ for 12h to obtain a cyclodextrin esterification intermediate;
(2) adding 18 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 80 parts by weight of melamine into 500 parts by weight of deionized water, stirring at the temperature of 95 ℃ for 90min at the rotating speed of 1200rpm, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at the temperature of 80 ℃ for 12h to obtain the pre-modified cyclodextrin.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying PP resin, glass fiber, pre-modified cyclodextrin and polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at the rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Example 4
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% of PP resin, 20 wt% of glass fiber, 20 wt% of modified cyclodextrin and 5 wt% of polyethylene polyoctene elastomer.
The modified cyclodextrin is prepared by the following method:
(1) adding 20 parts by weight of cyclodextrin into 100 parts by weight of phosphoric acid, stirring at the rotating speed of 800rpm for 20min, then placing into a reaction kettle with a polytetrafluoroethylene lining, placing into a drying oven at 100 ℃ for keeping for 1h, centrifuging after the reaction is finished, taking a bottom precipitate, washing, and drying in the drying oven at 60 ℃ for 12h to obtain a cyclodextrin esterification intermediate;
(2) adding 18 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 80 parts by weight of melamine into 500 parts by weight of deionized water, stirring at the temperature of 95 ℃ and the rotating speed of 1200rpm for 90min, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at the temperature of 80 ℃ for 12h to obtain pre-modified cyclodextrin;
(3) adding 15 parts by weight of the pre-modified cyclodextrin obtained in the step (2) and 5 parts by weight of polymethyltriethoxysilane into 100 parts by weight of absolute ethyl alcohol, then placing into a reaction kettle with a polytetrafluoroethylene lining, placing into an oven at 80 ℃ for 2 hours, centrifuging after the reaction is finished, taking the bottom precipitate for washing, and drying in the oven at 70 ℃ for 5 hours to obtain the modified cyclodextrin.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying the PP resin, the glass fiber, the modified cyclodextrin and the polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at the rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Example 5
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% of PP resin, 20 wt% of glass fiber, 20 wt% of modified cyclodextrin and 5 wt% of polyethylene polyoctene elastomer.
The modified cyclodextrin is prepared by the following method:
(1) adding 20 parts by weight of cyclodextrin into 100 parts by weight of phosphoric acid, stirring at the rotating speed of 800rpm for 20min, then placing into a reaction kettle with a polytetrafluoroethylene lining, placing into a drying oven at 100 ℃ for keeping for 1h, centrifuging after the reaction is finished, taking a bottom precipitate, washing, and drying in the drying oven at 60 ℃ for 12h to obtain a cyclodextrin esterification intermediate;
(2) adding 18 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 80 parts by weight of melamine into 500 parts by weight of deionized water, stirring at the temperature of 95 ℃ and the rotating speed of 1200rpm for 90min, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at the temperature of 80 ℃ for 12h to obtain pre-modified cyclodextrin;
(3) adding 15 parts by weight of the pre-modified cyclodextrin obtained in the step (2) and 5 parts by weight of 4-pyridyltriethoxysilane into 100 parts by weight of absolute ethyl alcohol, then placing the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven at 80 ℃ for 2 hours, centrifuging after the reaction is finished, taking the bottom precipitate for washing, and drying the bottom precipitate in the oven at 70 ℃ for 5 hours to obtain the modified cyclodextrin.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying the PP resin, the glass fiber, the modified cyclodextrin and the polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at the rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Example 6
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank comprises the following raw materials: 55 wt% of PP resin, 20 wt% of glass fiber, 20 wt% of modified cyclodextrin and 5 wt% of polyethylene polyoctene elastomer.
The modified cyclodextrin is prepared by the following method:
(1) adding 20 parts by weight of cyclodextrin into 100 parts by weight of phosphoric acid, stirring at the rotating speed of 800rpm for 20min, then placing into a reaction kettle with a polytetrafluoroethylene lining, placing into a drying oven at 100 ℃ for keeping for 1h, centrifuging after the reaction is finished, taking a bottom precipitate, washing, and drying in the drying oven at 60 ℃ for 12h to obtain a cyclodextrin esterification intermediate;
(2) adding 18 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 80 parts by weight of melamine into 500 parts by weight of deionized water, stirring at the temperature of 95 ℃ and the rotating speed of 1200rpm for 90min, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at the temperature of 80 ℃ for 12h to obtain pre-modified cyclodextrin;
(3) adding 15 parts by weight of the pre-modified cyclodextrin obtained in the step (2), 3 parts by weight of polymethyltriethoxysilane and 2 parts by weight of 4-pyridyltriethoxysilane into 100 parts by weight of absolute ethyl alcohol, then placing the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven at 80 ℃ for keeping for 2 hours, centrifuging after the reaction is finished, taking the bottom precipitate for washing, and drying in the oven at 70 ℃ for 5 hours to obtain the modified cyclodextrin.
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is prepared by the following method:
s1, drying the PP resin, the glass fiber, the modified cyclodextrin and the polyethylene polyoctene elastomer at 70 ℃ for 12 hours, weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 10 minutes at the rotating speed of 500rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, and drying at the temperature of 80 ℃ for 12 hours to obtain the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom guard plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the screw speed was 250rpm and the extrusion section operating temperature was 170 ℃.
Test example 1
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protection plate of the fuel tank of the automobile prepared in the examples 1 to 6 and the comparative example 1 was injection-molded by a plastic injection molding machine (nozzle temperature 230 ℃).
Limiting Oxygen Index (LOI) test: reference is made to the national standard GB/T2406.2-2009 part 2 of determination of combustion behaviour by oxygen index method for plastics: room temperature test (RT test). The specimen size was 80mm in length, 10mm in width and 4mm in thickness, conditioned at a temperature of 25 ℃ and a humidity of 40% for 24h, and a line was scribed at 50mm on the specimen. The test is carried out by adopting a JF-3 type oxygen index tester.
Vertical burning (UL-94) test: reference is made to GB/T2408 + 2008 'horizontal method and vertical method for measuring plastic combustion performance', wherein a test method B: vertical combustion (V). The sample size is 125mm long, 13mm wide and 3mm thick; the sample was conditioned for 24h at 25 ℃ and 40% humidity. The test was carried out using an SH5300 vertical combustion tester.
Each group of samples was tested five times and the average was taken as the test result.
TABLE 1 flame retardancy test results
From the above results, it can be seen that the addition of cyclodextrin in example 2 slightly improves the flame retardant properties of the composite material compared to example 1, probably due to the lower content of acid and gas sources in the material. The flame retardant property of the composite material of embodiment 3 is improved because the thermochemical reaction among the phosphoric acid, the melamine and the cyclodextrin in the pre-modified cyclodextrin produces a synergistic effect, and an effective carbon layer can be released to play a flame retardant role. Examples 4-6 with the crosslinker modified cyclodextrin, the flame retardancy of the composite was further improved, possibly for the following reasons: the modified cyclodextrin has stronger hydrophobicity, so that the dispersibility of the modified cyclodextrin in a PP matrix is better than that of the pre-modified cyclodextrin, and the cross-linking agent plays a certain promoting role in the process of carbon formation.
Test example 2
The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protection plate of the fuel tank of the automobile prepared in the examples 1 to 6 and the comparative example 1 was injection-molded by a plastic injection molding machine (nozzle temperature 230 ℃).
Testing the moisture barrier property: reference is made to GB/T1462-2005 "test method for Water absorption of fiber-reinforced plastics", in which method 2 is used for the test. The specific experimental method comprises the following steps: square pieces having a side length of 50mm and a thickness of 4mm were prepared as samples, and 5 samples were prepared for each set of examples; then the samples are put into a 50 ℃ oven for drying for 24h, moved into a dryer for cooling to room temperature, taken out and then weighed for each sample mass (m)1) (ii) a Soaking the weighed sample in boiling distilled water for 30min, cooling in distilled water at room temperature for 15min, taking out, removing surface water with clean filter paper, and weighing sample mass (m)2) (ii) a Measurement results Water absorption Capacity per unit surface area (m)s) Expressing, calculating the formula: m iss＝ma/S，ma＝m2-m1Wherein S is the initial total surface area of the sample in cm2，m1、m2、maHas the unit of g, msHas a unit of g/cm2. The moisture barrier property of the material is evaluated by the average unit surface area water absorption of the sample, and the smaller the value, the better the moisture barrier property. The results of the experiments are shown in the following table.
Table 2 moisture barrier property test results
The halogen-free flame retardant modified cyclodextrin adopted by the invention has smaller particle size, and particularly after the modification by the cross-linking agent, the surface of the cyclodextrin is converted into hydrophobicity, so that the compatibility among the modified cyclodextrin, the glass fiber and a PP matrix is greatly improved, the 'wick effect' of the glass fiber is weakened, the structure of the composite material is more compact, and the flame retardant property is improved while the moisture barrier property is also improved.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (3)
1. The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank is characterized by comprising the following raw materials: 18-23 wt% of glass fiber, 15-24 wt% of halogen-free flame retardant, 3-7 wt% of auxiliary agent and the balance of PP resin;
the halogen-free flame retardant is modified cyclodextrin;
the modified cyclodextrin is prepared by the following method:
(1) adding 18-22 parts by weight of cyclodextrin into 95-105 parts by weight of phosphoric acid, stirring for 15-30min at the rotation speed of 1000rpm of 600-;
(2) adding 17-21 parts by weight of the cyclodextrin esterification intermediate obtained in the step (1) and 75-85 parts by weight of melamine into 480-520 parts by weight of deionized water, stirring at 90-100 ℃ and 1500rpm for 80-100min, centrifuging after the reaction is finished, taking the bottom precipitate, washing, and drying in an oven at 70-90 ℃ for 10-15h to obtain pre-modified cyclodextrin;
(3) adding 13-18 parts by weight of the pre-modified cyclodextrin obtained in the step (2) and 3-8 parts by weight of a cross-linking agent into 90-110 parts by weight of absolute ethyl alcohol, then placing the mixture into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a 75-85 ℃ drying oven for 1.5-2.5h, centrifuging after the reaction is finished, taking bottom precipitate, washing, and drying in the 60-80 ℃ drying oven for 4-6h to obtain modified cyclodextrin;
the cross-linking agent is a mixture of polymethyl triethoxy silane and 4-pyridine triethoxy silane, and the mass ratio of the polymethyl triethoxy silane to the 4-pyridine triethoxy silane is 3: (1-3).
2. The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the fuel tank of the automobile according to claim 1, wherein the auxiliary agent is any one of a polyethylene/polyoctenamer elastomer, a polylactic acid/polyurethane elastomer and a polypropylene/polystyrene elastomer.
3. The halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank as claimed in any one of claims 1-2, which is prepared by the following method:
s1, drying the PP resin, the glass fiber, the halogen-free flame retardant and the auxiliary agent for 10-15h at 65-75 ℃, then weighing the components according to the proportion, and putting the components into a high-speed mixer to mix for 5-15min at the rotation speed of 400-600rpm to obtain a mixture;
s2, putting the mixture obtained in the step S1 into a double-screw extruder, performing melt extrusion granulation, conveying the granulated material into a storage bin through an air conveying system, drying at the temperature of 75-85 ℃ for 10-15 hours, and obtaining the halogen-free flame-retardant long glass fiber reinforced PP composite material for the bottom protective plate of the automobile fuel tank, wherein the extrusion process conditions are as follows: the rotation speed of the screw is 150-300rpm, and the working temperature of the extrusion section is 120-210 ℃.
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Application publication date: 20210702 Assignee: Guangdong Rongtong Financial Leasing Co.,Ltd. Assignor: Guangdong Yuhao New Material Technology Co.,Ltd. Contract record no.: X2022980013986 Denomination of invention: Halogen-free flame retardant long glass fiber reinforced PP composite material for automobile fuel tank bottom guard Granted publication date: 20220329 License type: Exclusive License Record date: 20220902 |
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Denomination of invention: Halogen-free flame retardant long glass fiber reinforced PP composite material for automobile fuel tank bottom guard Effective date of registration: 20220906 Granted publication date: 20220329 Pledgee: Guangdong Rongtong Financial Leasing Co.,Ltd. Pledgor: Guangdong Yuhao New Material Technology Co.,Ltd. Registration number: Y2022980014581 |
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