CN116836483A - Flame-retardant composite material for high-toughness battery outer cover and preparation method thereof - Google Patents
Flame-retardant composite material for high-toughness battery outer cover and preparation method thereof Download PDFInfo
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- CN116836483A CN116836483A CN202310816798.6A CN202310816798A CN116836483A CN 116836483 A CN116836483 A CN 116836483A CN 202310816798 A CN202310816798 A CN 202310816798A CN 116836483 A CN116836483 A CN 116836483A
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- flame retardant
- outer cover
- battery outer
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- toughness
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- 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 88
- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 49
- 239000004743 Polypropylene Substances 0.000 claims abstract description 42
- 229920001155 polypropylene Polymers 0.000 claims abstract description 42
- -1 polypropylene Polymers 0.000 claims abstract description 41
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 27
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000005457 ice water Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 12
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000017 hydrogel Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000005491 wire drawing Methods 0.000 claims description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 239000000155 melt Substances 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a flame-retardant composite material for a high-toughness battery outer cover and a preparation method thereof, belonging to the technical field of composite materials, and comprising the following raw materials in parts by weight: 20-40 parts of recycled polypropylene, 12-25 parts of polypropylene, 5-10 parts of chlorinated polyethylene, 5-10 parts of composite flame retardant, 5-15 parts of activated modified barium sulfate, 0.5-1 part of antioxidant, 0.3-1 part of lubricant and 0.2-0.5 part of anti-dripping agent; the recycled polypropylene, the chlorinated polyethylene, the activated modified barium sulfate and the like are compounded to obtain the high-toughness flame-retardant composite material for the battery outer cover, which is beneficial to improving the impact strength and the elongation at break of the composite material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a flame-retardant composite material for a high-toughness battery outer cover and a preparation method thereof.
Background
Polypropylene (PP) is a universal resin, is light and nontoxic, has the advantages of excellent electrical insulation property, chemical corrosion resistance, convenient molding and processing, low price and the like, and is widely applied to industries of electric appliances, chemical industry, machinery, textile, construction, furniture, food packaging and the like; however, PP is a flammable material, its oxygen index is only 17.4-18.5, and a large number of droplets are generated during combustion, so that flame is easily propagated, which limits the application of PP in many fields.
With the development of new energy electric vehicles, the power battery is used as a core part of the new energy electric vehicle, the safety of the power battery directly influences the safety of the whole vehicle, the power battery system of the pure electric vehicle is generally arranged below a vehicle body bottom plate, a relatively harsh installation environment exists, a battery box body and a cover plate are used as carriers of the power battery, the safety work and protection of a battery pack are key, the safety, the reliability and the durability of the battery pack are very important, and the performance of the whole vehicle is determined.
At present, the traditional battery box body and the cover plate are made of metal materials, such as steel or aluminum alloy, but the weight of the metal battery box body and the cover plate is heavy, so that the energy efficiency ratio of the battery can be reduced; poor tightness can cause the battery box body to be immersed in water to cause short circuit of the battery; the corrosion resistance is poor, so that the battery box body and the cover plate are easy to corrode; in addition, the method has the defects of complex processing technology, low collision strength and the like, and the weight reduction of the automobile cannot be realized; the battery box body, the cover plate and the like can also adopt resin-based fiber reinforced materials, in particular PP fireproof filling materials, and the performances of the materials such as specific strength, specific rigidity, buffer resistance, corrosion resistance and the like are greatly superior to those of metal materials, so that the corrosion resistance and weight reduction effects are obvious, and the material is an ideal material for the battery box body and the cover plate for the electric automobile in the future; therefore, the flame retardant modification of polypropylene is generally realized by adding an external flame retardant, and the mechanical property of the material is reduced by adding a large amount of flame retardant, so that the technical problem to be solved is how to endow the polypropylene with excellent flame retardant property while not reducing the mechanical property of the polypropylene material.
Disclosure of Invention
In order to solve the technical problems, the invention provides a flame-retardant composite material for a high-toughness battery outer cover and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the flame-retardant composite material for the high-toughness battery outer cover comprises the following raw materials in parts by weight: 20-40 parts of recycled polypropylene, 12-25 parts of polypropylene, 5-10 parts of chlorinated polyethylene, 5-10 parts of composite flame retardant, 5-15 parts of activated modified barium sulfate, 0.5-1 part of antioxidant, 0.3-1 part of lubricant and 0.2-0.5 part of anti-dripping agent;
the recycled polypropylene is copolymerized polypropylene, the melt flow rate is less than 3g/10 min under the condition of 230 ℃ and 2.16kg, and the density is less than or equal to 0.92g/cm 3 ；
The polypropylene is high impact polypropylene, the melt flow rate is less than or equal to 1.5g/10 min under the condition of 230 ℃ and 2.16kg, and the notch impact strength is NB kJ/m 2 ；
The chlorinated polyethylene is CPE, the melt flow rate is less than or equal to 2g/10 min under the condition of 190 ℃ and 2.16kg, and the elongation at break is more than or equal to 450%;
the composite flame retardant comprises the following steps:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment on the graphene oxide under ice water bath for 30min to prepare dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding boric acid aqueous solution with the mass fraction of 10%, heating to 180 ℃, preserving heat for 4h, adding a flame retardant to prepare a hydrogel precursor, carrying out vacuum freeze drying to prepare a composite flame retardant, and controlling the weight ratio of the dispersion liquid, the boric acid aqueous solution and the flame retardant to be 5-6:1:3.
In the step S4, a hydrothermal reduction method is adopted to prepare a three-dimensional graphene porous structure, boron is introduced in the preparation process, and the boron is introduced into the prepared three-dimensional graphene porous structure to serve as a carrier, so that on one hand, the specific surface area of the carrier is improved through a special three-dimensional and porous structure, the adsorption performance is improved, a large amount of flame retardants can be adsorbed, and the doped boron can also play a role in synergetic flame retardance.
Further: the flame retardant comprises the following steps:
s1, adding hexachlorotriphosphazene and acetone into a four-necked flask under nitrogen atmosphere, stirring at a constant speed for 15min in an ice water bath, slowly adding an acetone solution of 4-amino-2, 6-tetramethylpiperidine, reacting for 1h in an ice water bath under heat preservation, heating and refluxing for 12h after the dripping is finished, and removing a solvent by rotary evaporation after the reaction is finished to prepare an intermediate 1;
in the step S1, hexachlorotriphosphazene reacts with 4-amino-2, 6-tetramethylpiperidine to generate an intermediate 1, wherein the structure of the intermediate 1 is shown as follows:
s2, adding the intermediate 1, magnesium hydroxide and deionized water into a four-neck flask under nitrogen atmosphere, heating to 65 ℃, slowly dropwise adding 30% hydrogen peroxide aqueous solution by mass fraction, reacting for 10 hours under heat preservation, adding chloroform for extraction after the reaction is finished, washing with deionized water, and removing the solvent by rotary evaporation to obtain an intermediate 2;
and S3, adding the intermediate 2, acetonitrile and cyclohexane into a four-neck flask under nitrogen atmosphere, stirring at a constant speed, sequentially adding ferrous sulfate heptahydrate, glacial acetic acid and tetrabutylammonium bromide, heating to 50 ℃, continuously stirring for 30min, heating to 60 ℃, slowly dropwise adding 30% hydrogen peroxide aqueous solution by mass fraction, continuously reacting for 3h after the dropwise adding is finished, distilling the generated reaction solution under reduced pressure at 50 ℃ after the reaction is finished, adding deionized water and methyl tert-butyl ether for extraction, washing with deionized water until the washing solution is neutral, and drying to obtain the flame retardant.
In the step S2, firstly, the synthesized intermediate 1 is treated, imino groups are changed into nitroxide free radicals, the intermediate 2 is prepared, and then in the step S3, ferrous sulfate heptahydrate and hydrogen peroxide are used as an oxidation-reduction system, tetrabutylammonium bromide is used as a phase transfer catalyst, and a flame retardant is prepared, wherein the reaction mechanism is as follows:
according to the flame retardant, hexachloro-triphosphazene is used as a matrix, and has excellent flame retardant performance, but halogen elements are not in accordance with the environmental protection requirement.
Further: the dosage ratio of hexachlorotriphosphazene, 4-amino-2, 6-tetramethylpiperidine and acetone is controlled to be 0.04mmo l to 0.24mmo l to 30mL in the step S1, the dosage ratio of the intermediate 1, magnesium hydroxide, aqueous hydrogen peroxide solution and deionized water is controlled to be 0.1mmo l to 4-5mg to 1.5-2.0mL to 20mL in the step S2, and the dosage ratio of the intermediate 2, acetonitrile, cyclohexane, ferrous sulfate heptahydrate, glacial acetic acid, tetrabutylammonium bromide and aqueous hydrogen peroxide solution is controlled to be 0.05mmo l to 20mL to 0.6mmo l to 0.001mmo l to 0.003mmo l to 0.002mmo l to 0.5mL in the step S3.
Further, in the step S1, the acetone solution of the 4-amino-2, 6-tetramethylpiperidine is prepared by mixing the 4-amino-2, 6-tetramethylpiperidine and acetone according to the dosage ratio of 0.24mmol to 50 mL.
Further: the activated modified barium sulfate comprises the following steps:
adding barium sulfate into a high-speed mixer, heating to 110-120 ℃, stirring at a high speed for 3-5min, sequentially adding nano aluminum oxide and sodium stearate, continuously stirring for 5-7min, discharging, and obtaining activated modified barium sulfate, wherein the weight ratio of the barium sulfate to the nano aluminum oxide to the sodium stearate is controlled to be 100:1.5-2:1-1.5, and the particle size of the barium sulfate is less than or equal to 2 mu m.
Further: the antioxidant is formed by mixing one or more of antioxidant THP-24, antioxidant RC 626 and antioxidant 1010 according to any proportion.
Further: the lubricant is prepared by mixing one or more of erucamide, pentaerythritol stearate and chlorinated polyethylene wax according to any proportion.
Further: the anti-dripping agent is modified polytetrafluoroethylene powder, and the molecular weight of the anti-dripping agent is 4-5 million.
A preparation method of a flame-retardant composite material for a high-toughness battery outer cover comprises the following steps:
firstly, weighing raw materials of the components according to the formula proportion, and adding the raw materials into a high-speed stirrer to stir for 3-5min to prepare a mixture;
and secondly, adding the prepared mixture into a double-screw extruder for mixing, and performing melt extrusion, wire drawing, water cooling, air drying and granulating to prepare the flame-retardant composite material for the high-toughness battery outer cover.
Wherein, the temperature of the twin-screw extruder is set as: (1) zone: 165-180 ℃; (2) zone: 190-200 ℃; (3) the temperature of the zone is 200-210 ℃; (4) zone: 210-220 ℃; (5) zone: 200-210 ℃; (6) zone: 200-210 ℃; (7) zone: 190-200 ℃; (8) zone: 180-190 ℃; (9) zone: 190-200 ℃; the rotating speed of the screw is controlled to be 300-420 r/min, and the frequency of the feeding machine is 10-28Hz.
The invention has the beneficial effects that:
the recycled PP adopted by the invention greatly improves the utilization rate of waste PP materials, reduces environmental pollution, and more importantly, reduces the cost of the composite material and improves the market competitiveness; by adding the activated modified barium sulfate, the smoothness and flatness of the surface of the material, the impact property and the elongation at break of the material are not affected, which are not possessed by other filling powder.
According to the invention, the recycled polypropylene, the chlorinated polyethylene, the activated modified barium sulfate and the like are compounded to obtain the high-toughness battery outer cover flame-retardant composite material, so that the impact strength and the elongation at break of the composite material are improved, the production efficiency of secondary plastic suction molding after extrusion molding is improved, the production cost and the reject ratio are reduced, the composite flame retardant is prepared, a three-dimensional graphene porous structure is synthesized in the preparation process of the flame retardant, boron is introduced as a carrier in the preparation process of the flame retardant, on one hand, the specific surface area of the carrier is improved through the special three-dimensional and porous structure, the adsorption performance is improved, a large amount of the flame retardant can be adsorbed, the doped boron also has a synergistic flame-retardant function, the flame retardant synthesized by loading the flame retardant is realized, the synergistic flame retardance of a plurality of elements including nitrogen, phosphorus and boron is realized, and the flame retardance is improved through the special lamellar structure, and the excellent flame retardant performance can be endowed to a polypropylene substrate without adding a large amount of flame retardant.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The composite flame retardant comprises the following steps:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment on the graphene oxide under ice water bath for 30min to prepare dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding boric acid aqueous solution with the mass fraction of 10%, heating to 180 ℃, preserving heat for 4h, adding a flame retardant to prepare a hydrogel precursor, carrying out vacuum freeze drying to prepare a composite flame retardant, and controlling the weight ratio of the dispersion liquid, the boric acid aqueous solution and the flame retardant to be 5:1:3.
The flame retardant comprises the following steps:
s1, adding hexachlorotriphosphazene and acetone into a four-neck flask under nitrogen atmosphere, stirring at a constant speed for 15min in an ice water bath, slowly adding an acetone solution of 4-amino-2, 6-tetramethylpiperidine, performing heat preservation reaction for 1h in the ice water bath, heating and refluxing for 12h after the dripping is finished, and performing rotary evaporation to remove a solvent after the reaction is finished to prepare an intermediate 1, wherein the dosage ratio of the hexachlorotriphosphazene, the 4-amino-2, 6-tetramethylpiperidine and the acetone is controlled to be 0.04 mmol:0.24 mmol:30 mL;
the acetone solution of the 4-amino-2, 6-tetramethylpiperidine is prepared by mixing 4-amino-2, 6-tetramethylpiperidine and acetone according to the dosage ratio of 0.24mmol to 50 mL.
S2, adding the intermediate 1, magnesium hydroxide and deionized water into a four-neck flask under nitrogen atmosphere, heating to 65 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, carrying out heat preservation reaction for 10 hours, adding chloroform for extraction after the reaction is finished, washing with deionized water, and carrying out rotary evaporation to remove a solvent to obtain the intermediate 2, wherein the dosage ratio of the intermediate 1, the magnesium hydroxide, the hydrogen peroxide aqueous solution and the deionized water is controlled to be 0.1 mmol:4 mg:1.5 mL:20 mL;
and S3, adding the intermediate 2, acetonitrile and cyclohexane into a four-neck flask under nitrogen atmosphere, stirring at a constant speed, sequentially adding ferrous sulfate heptahydrate, glacial acetic acid and tetrabutylammonium bromide, heating to 50 ℃, continuously stirring for 30min, heating to 60 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, continuously reacting for 3h after the dropwise adding is finished, decompressing and distilling the generated reaction solution at 50 ℃, adding deionized water and methyl tert-butyl ether for extraction, washing with deionized water until a washing solution is neutral, drying, and obtaining the flame retardant, wherein the dosage ratio of the intermediate 2, acetonitrile, cyclohexane, ferrous sulfate heptahydrate, glacial acetic acid, tetrabutylammonium bromide and hydrogen peroxide aqueous solution is controlled to be 0.05mmo l to 20mL to 0.6mmo l to 0.003mmo l to 0.002mmo l to 0.5mL.
Example 2
The composite flame retardant comprises the following steps:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment on the graphene oxide under ice water bath for 30min to prepare dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding boric acid aqueous solution with the mass fraction of 10%, heating to 180 ℃, preserving heat for 4h, adding a flame retardant to prepare a hydrogel precursor, carrying out vacuum freeze drying to prepare a composite flame retardant, and controlling the weight ratio of the dispersion liquid, the boric acid aqueous solution and the flame retardant to be 5.5:1:3.
The flame retardant comprises the following steps:
s1, adding hexachlorotriphosphazene and acetone into a four-neck flask under nitrogen atmosphere, stirring at a constant speed for 15min in an ice water bath, slowly adding an acetone solution of 4-amino-2, 6-tetramethylpiperidine, performing heat preservation reaction for 1h in the ice water bath, heating and refluxing for 12h after the dripping is finished, and performing rotary evaporation to remove a solvent after the reaction is finished to prepare an intermediate 1, wherein the dosage ratio of the hexachlorotriphosphazene, the 4-amino-2, 6-tetramethylpiperidine and the acetone is controlled to be 0.04 mmol:0.24 mmol:30 mL;
the acetone solution of the 4-amino-2, 6-tetramethylpiperidine is prepared by mixing 4-amino-2, 6-tetramethylpiperidine and acetone according to the dosage ratio of 0.24mmol to 50 mL.
S2, adding the intermediate 1, magnesium hydroxide and deionized water into a four-neck flask under nitrogen atmosphere, heating to 65 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, carrying out heat preservation reaction for 10 hours, adding chloroform for extraction after the reaction is finished, washing with deionized water, and carrying out rotary evaporation to remove a solvent to obtain the intermediate 2, wherein the dosage ratio of the intermediate 1, the magnesium hydroxide, the hydrogen peroxide aqueous solution and the deionized water is controlled to be 0.1 mmol:4.5 mg:1.8 mL:20 mL;
and S3, adding the intermediate 2, acetonitrile and cyclohexane into a four-neck flask under nitrogen atmosphere, stirring at a constant speed, sequentially adding ferrous sulfate heptahydrate, glacial acetic acid and tetrabutylammonium bromide, heating to 50 ℃, continuously stirring for 30min, heating to 60 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, continuously reacting for 3h after the dropwise adding is finished, decompressing and distilling the generated reaction solution at 50 ℃, adding deionized water and methyl tert-butyl ether for extraction, washing with deionized water until a washing solution is neutral, drying, and obtaining the flame retardant, wherein the dosage ratio of the intermediate 2, acetonitrile, cyclohexane, ferrous sulfate heptahydrate, glacial acetic acid, tetrabutylammonium bromide and hydrogen peroxide aqueous solution is controlled to be 0.05mmo l to 20mL to 0.6mmo l to 0.003mmo l to 0.002mmo l to 0.5mL.
Example 3
The composite flame retardant comprises the following steps:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment on the graphene oxide under ice water bath for 30min to prepare dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding boric acid aqueous solution with the mass fraction of 10%, heating to 180 ℃, preserving heat for 4h, adding a flame retardant to prepare a hydrogel precursor, carrying out vacuum freeze drying to prepare a composite flame retardant, and controlling the weight ratio of the dispersion liquid, the boric acid aqueous solution and the flame retardant to be 6:1:3.
The flame retardant comprises the following steps:
s1, adding hexachlorotriphosphazene and acetone into a four-neck flask under nitrogen atmosphere, stirring at a constant speed for 15min in an ice water bath, slowly adding an acetone solution of 4-amino-2, 6-tetramethylpiperidine, performing heat preservation reaction for 1h in the ice water bath, heating and refluxing for 12h after the dripping is finished, and performing rotary evaporation to remove a solvent after the reaction is finished to prepare an intermediate 1, wherein the dosage ratio of the hexachlorotriphosphazene, the 4-amino-2, 6-tetramethylpiperidine and the acetone is controlled to be 0.04 mmol:0.24 mmol:30 mL;
the acetone solution of the 4-amino-2, 6-tetramethylpiperidine is prepared by mixing 4-amino-2, 6-tetramethylpiperidine and acetone according to the dosage ratio of 0.24mmol to 50 mL.
S2, adding the intermediate 1, magnesium hydroxide and deionized water into a four-neck flask under nitrogen atmosphere, heating to 65 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, carrying out heat preservation reaction for 10 hours, adding chloroform for extraction after the reaction is finished, washing with deionized water, and carrying out rotary evaporation to remove a solvent to obtain an intermediate 2, wherein the dosage ratio of the intermediate 1, the magnesium hydroxide, the hydrogen peroxide aqueous solution and the deionized water is controlled to be 0.1 mmol:5 mg:2.0 mL:20 mL;
and S3, adding the intermediate 2, acetonitrile and cyclohexane into a four-neck flask under nitrogen atmosphere, stirring at a constant speed, sequentially adding ferrous sulfate heptahydrate, glacial acetic acid and tetrabutylammonium bromide, heating to 50 ℃, continuously stirring for 30min, heating to 60 ℃, slowly dropwise adding 30% by mass of hydrogen peroxide aqueous solution, continuously reacting for 3h after the dropwise adding is finished, decompressing and distilling the generated reaction solution at 50 ℃, adding deionized water and methyl tert-butyl ether for extraction, washing with deionized water until a washing solution is neutral, drying, and obtaining the flame retardant, wherein the dosage ratio of the intermediate 2, acetonitrile, cyclohexane, ferrous sulfate heptahydrate, glacial acetic acid, tetrabutylammonium bromide and hydrogen peroxide aqueous solution is controlled to be 0.05mmo l to 20mL to 0.6mmo l to 0.003mmo l to 0.002mmo l to 0.5mL.
Example 4
The flame-retardant composite material for the high-toughness battery outer cover comprises the following raw materials in parts by weight: 20 parts of recycled polypropylene, 12 parts of polypropylene, 5 parts of chlorinated polyethylene, 5 parts of the composite flame retardant prepared in example 1, 5 parts of activated modified barium sulfate, 0.5 part of antioxidant THP-24,0.3 parts of lubricant erucamide and 0.2 part of anti-dripping agent;
the flame-retardant composite material for the high-toughness battery outer cover comprises the following steps:
firstly, weighing raw materials of all components according to the formula proportion, and adding the raw materials into a high-speed stirrer to stir for 3 min to prepare a mixture;
and secondly, adding the prepared mixture into a double-screw extruder for mixing, and performing melt extrusion, wire drawing, water cooling, air drying and granulating to prepare the flame-retardant composite material for the high-toughness battery outer cover.
Wherein, the temperature of the twin-screw extruder is set as: (1) zone: 165-180 ℃; (2) zone: 190-200 ℃; (3) the temperature of the zone is 200-210 ℃; (4) zone: 210-220 ℃; (5) zone: 200-210 ℃; (6) zone: 200-210 ℃; (7) zone: 190-200 ℃; (8) zone: 180-190 ℃; (9) zone: 190-200 ℃; the rotating speed of the screw is controlled to be 300-420 r/min, and the frequency of the feeding machine is 10-28Hz.
The recycled polypropylene is copolymerized polypropylene, the melt flow rate is less than 3g/10 min under the condition of 230 ℃ and 2.16kg, and the density is less than or equal to 0.92g/cm 3 ；
The polypropylene is high impact polypropylene, the melt flow rate is less than or equal to 1.5g/10 min under the condition of 230 ℃ and 2.16kg, and the notch impact strength is NB kJ/m 2 ；
The chlorinated polyethylene is CPE, the melt flow rate is less than or equal to 2g/10 min under the condition of 190 ℃ and 2.16kg, and the elongation at break is more than or equal to 450%;
the activated modified barium sulfate comprises the following steps:
adding barium sulfate into a high-speed mixer, heating to 110 ℃, stirring at a high speed for 3 min, sequentially adding nano aluminum oxide and sodium stearate, continuously stirring for 5min, discharging, and obtaining activated modified barium sulfate, wherein the weight ratio of the barium sulfate to the nano aluminum oxide to the sodium stearate is controlled to be 100:1.5:1, and the particle size of the barium sulfate is less than or equal to 2 mu m.
The anti-dripping agent is modified polytetrafluoroethylene powder (novel Iyasu material) with molecular weight of 4-5 million.
Example 5
The flame-retardant composite material for the high-toughness battery outer cover comprises the following raw materials in parts by weight: 30 parts of recycled polypropylene, 20 parts of polypropylene, 8 parts of chlorinated polyethylene, 8 parts of the composite flame retardant prepared in example 1, 10 parts of activated modified barium sulfate, 0.8 part of antioxidant RC 626,0.5 parts of lubricant pentaerythritol stearate and 0.3 part of anti-dripping agent;
the flame-retardant composite material for the high-toughness battery outer cover comprises the following steps:
firstly, weighing raw materials of all components according to the formula proportion, and adding the raw materials into a high-speed stirrer to stir for 4 min to prepare a mixture;
and secondly, adding the prepared mixture into a double-screw extruder for mixing, and performing melt extrusion, wire drawing, water cooling, air drying and granulating to prepare the flame-retardant composite material for the high-toughness battery outer cover.
Wherein, the temperature of the twin-screw extruder is set as: (1) zone: 165-180 ℃; (2) zone: 190-200 ℃; (3) the temperature of the zone is 200-210 ℃; (4) zone: 210-220 ℃; (5) zone: 200-210 ℃; (6) zone: 200-210 ℃; (7) zone: 190-200 ℃; (8) zone: 180-190 ℃; (9) zone: 190-200 ℃; the rotating speed of the screw is controlled to be 300-420 r/min, and the frequency of the feeding machine is 10-28Hz.
The recycled polypropylene is copolymerized polypropylene, the melt flow rate is less than 3g/10 min under the condition of 230 ℃ and 2.16kg, and the density is less than or equal to 0.92g/cm 3 ；
The polypropylene is high impact polypropylene, the melt flow rate is less than or equal to 1.5g/10 min under the condition of 230 ℃ and 2.16kg, and the notch impact strength is NB kJ/m 2 ；
The chlorinated polyethylene is CPE, the melt flow rate is less than or equal to 2g/10 min under the condition of 190 ℃ and 2.16kg, and the elongation at break is more than or equal to 450%;
the activated modified barium sulfate comprises the following steps:
adding barium sulfate into a high-speed mixer, heating to 115 ℃, stirring at a high speed for 4 min, sequentially adding nano aluminum oxide and sodium stearate, continuously stirring for 6 min, discharging, and obtaining activated modified barium sulfate, wherein the weight ratio of the barium sulfate to the nano aluminum oxide to the sodium stearate is controlled to be 100:1.8:1.2, and the particle size of the barium sulfate is less than or equal to 2 mu m.
The anti-dripping agent is modified polytetrafluoroethylene powder (novel Iyasu material) with molecular weight of 4-5 million.
Example 6
The flame-retardant composite material for the high-toughness battery outer cover comprises the following raw materials in parts by weight: 40 parts of recycled polypropylene, 25 parts of polypropylene, 10 parts of chlorinated polyethylene, 10 parts of activated modified barium sulfate, 15 parts of the composite flame retardant prepared in example 3, 1 part of antioxidant 1010,1 parts of lubricant chlorinated polyethylene wax and 0.5 part of anti-dripping agent;
the flame-retardant composite material for the high-toughness battery outer cover comprises the following steps:
firstly, weighing raw materials of all components according to the formula proportion, and adding the raw materials into a high-speed stirrer to stir 5min to prepare a mixture;
and secondly, adding the prepared mixture into a double-screw extruder for mixing, and performing melt extrusion, wire drawing, water cooling, air drying and granulating to prepare the flame-retardant composite material for the high-toughness battery outer cover.
Wherein, the temperature of the twin-screw extruder is set as: (1) zone: 165-180 ℃; (2) zone: 190-200 ℃; (3) the temperature of the zone is 200-210 ℃; (4) zone: 210-220 ℃; (5) zone: 200-210 ℃; (6) zone: 200-210 ℃; (7) zone: 190-200 ℃; (8) zone: 180-190 ℃; (9) zone: 190-200 ℃; the rotating speed of the screw is controlled to be 300-420 r/min, and the frequency of the feeding machine is 10-28Hz.
The recycled polypropylene is copolymerized polypropylene, the melt flow rate is less than 3g/10 min under the condition of 230 ℃ and 2.16kg, and the density is less than or equal to 0.92g/cm 3 ；
The polypropylene is high impact polypropylene, the melt flow rate is less than or equal to 1.5g/10 min under the condition of 230 ℃ and 2.16kg, and the notch impact strength is NB kJ/m 2 ；
The chlorinated polyethylene is CPE, the melt flow rate is less than or equal to 2g/10 min under the condition of 190 ℃ and 2.16kg, and the elongation at break is more than or equal to 450%;
the activated modified barium sulfate comprises the following steps:
adding barium sulfate into a high-speed mixer, heating to 120 ℃, stirring at a high speed for 5min, sequentially adding nano aluminum oxide and sodium stearate, continuously stirring for 7min, discharging, and obtaining activated modified barium sulfate, wherein the weight ratio of the barium sulfate to the nano aluminum oxide to the sodium stearate is controlled to be 100:2:1.5, and the particle size of the barium sulfate is less than or equal to 2 mu m.
The anti-dripping agent is modified polytetrafluoroethylene powder (novel Iyasu material) with molecular weight of 4-5 million.
Comparative example 1
Compared with the comparative example 4, the preparation method using graphene oxide loaded boron as the flame retardant is as follows:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment on the graphene oxide under ice water bath for 30min to prepare dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding 10% boric acid aqueous solution by mass percent, heating to 180 ℃, preserving heat for 12h to prepare a hydrogel precursor, carrying out vacuum freeze drying to prepare a composite flame retardant, and controlling the weight ratio of the dispersion liquid to the boric acid aqueous solution to be 6:1.
The procedure is as in example 4.
Comparative example 2
In this comparative example, the composite flame retardant was replaced with the flame retardant synthesized in example 1, as compared with example 4.
Comparative example 3
The comparative example is a flame retardant polypropylene material produced by a commercial company.
The properties of the materials prepared in examples 4 to 6 and comparative examples 1 to 3 were examined, and the results are shown in Table 1 below:
(1) Tensile strength and elongation at break test: i O527 standard;
(2) Melt flow rate test: i SO 1133 standard, test conditions are 230 ℃, 2.16kg;
(3) Notched impact strength test: i SO 180 standard;
(4) Flame retardancy test: GB/T2406.2-2009;
TABLE 1
From the above Table 1, it can be seen that the polypropylene materials prepared in examples 4 to 6 of the present invention have excellent mechanical properties and flame retardant properties.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. A flame-retardant composite material for a high-toughness battery outer cover is characterized in that: comprises the following raw materials in parts by weight: 20-40 parts of recycled polypropylene, 12-25 parts of polypropylene, 5-10 parts of chlorinated polyethylene, 5-10 parts of composite flame retardant, 5-15 parts of activated modified barium sulfate, 0.5-1 part of antioxidant, 0.3-1 part of lubricant and 0.2-0.5 part of anti-dripping agent;
the composite flame retardant comprises the following steps:
adding graphene oxide prepared by a Hummers method into deionized water, carrying out ultrasonic treatment for 30min in an ice water bath to prepare a dispersion liquid with the concentration of 5mg/mL, transferring the dispersion liquid into a liner of a reaction kettle, adding a boric acid aqueous solution with the mass fraction of 10%, heating to 180 ℃, preserving heat for 4h, adding a flame retardant, preparing a hydrogel precursor, and carrying out vacuum freeze drying to prepare the composite flame retardant.
2. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the weight ratio of the dispersion liquid, the boric acid aqueous solution and the flame retardant is controlled to be 5-6:1:3.
3. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the flame retardant comprises the following steps:
s1, adding hexachlorotriphosphazene and acetone into a four-neck flask under nitrogen atmosphere, stirring for 15min at constant speed in ice water bath, slowly adding an acetone solution of 4-amino-2, 6-tetramethylpiperidine, reacting for 1h in ice water bath under heat preservation, heating and refluxing for 12h after the dripping is finished, and removing the solvent by rotary evaporation after the reaction is finished to prepare an intermediate 1;
s2, adding the intermediate 1, magnesium hydroxide and deionized water into a four-neck flask under nitrogen atmosphere, heating to 65 ℃, slowly dropwise adding 30% hydrogen peroxide aqueous solution by mass fraction, reacting for 10 hours under heat preservation, adding chloroform for extraction after the reaction is finished, washing with deionized water, and removing the solvent by rotary evaporation to obtain an intermediate 2;
and S3, adding the intermediate 2, acetonitrile and cyclohexane into a four-neck flask under nitrogen atmosphere, stirring at a constant speed, sequentially adding ferrous sulfate heptahydrate, glacial acetic acid and tetrabutylammonium bromide, heating to 50 ℃, continuously stirring for 30min, heating to 60 ℃, slowly dropwise adding 30% by mass of aqueous hydrogen peroxide solution, continuously reacting for 3h after the dropwise adding is finished, distilling the generated reaction solution under reduced pressure at 50 ℃ after the reaction is finished, adding deionized water and methyl tert-butyl ether for extraction, washing with deionized water until the washing solution is neutral, and drying to obtain the flame retardant.
4. A flame retardant composite for a high toughness battery outer cover according to claim 3, wherein: the dosage ratio of hexachlorotriphosphazene, 4-amino-2, 6-tetramethylpiperidine and acetone is controlled to be 0.04mmol to 0.24mmol to 30mL in the step S1, the dosage ratio of the intermediate 1, magnesium hydroxide, aqueous hydrogen peroxide solution and deionized water is controlled to be 0.1mmol to 4-5mg to 1.5-2.0mL to 20mL in the step S2, and the dosage ratio of the intermediate 2, acetonitrile, cyclohexane, ferrous sulfate heptahydrate, glacial acetic acid, tetrabutylammonium bromide and aqueous hydrogen peroxide solution is controlled to be 0.05mmol to 20mL to 0.6mmol to 0.001mmol to 0.003mmol to 0.002mmol to 0.5mL in the step S3.
5. A flame retardant composite for a high toughness battery outer cover according to claim 3, wherein: the acetone solution of the 4-amino-2, 6-tetramethylpiperidine in the step S1 is prepared by mixing 4-amino-2, 6-tetramethylpiperidine and acetone according to the dosage ratio of 0.24mmol to 50 mL.
6. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the activated modified barium sulfate comprises the following steps:
adding barium sulfate into a high-speed mixer, heating to 110-120 ℃, stirring at a high speed for 3-5min, sequentially adding nano aluminum oxide and sodium stearate, continuously stirring for 5-7min, discharging, and obtaining activated modified barium sulfate, wherein the weight ratio of the barium sulfate to the nano aluminum oxide to the sodium stearate is controlled to be 100:1.5-2:1-1.5, and the particle size of the barium sulfate is less than or equal to 2 mu m.
7. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the antioxidant is formed by mixing one or more of antioxidant THP-24, antioxidant RC 626 and antioxidant 1010 according to any proportion.
8. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the lubricant is prepared by mixing one or more of erucamide, pentaerythritol stearate and chlorinated polyethylene wax according to any proportion.
9. The flame retardant composite for high toughness battery outer cover according to claim 1, wherein: the anti-dripping agent is modified polytetrafluoroethylene powder, and the molecular weight of the anti-dripping agent is 4-5 million.
10. The method for preparing the flame retardant composite material for the high-toughness battery outer cover, according to claim 1, is characterized in that: the method comprises the following steps:
firstly, weighing raw materials of all components according to the formula proportion, and adding the raw materials into a high-speed stirrer to stir for 3-5min to prepare a mixture;
and secondly, adding the prepared mixture into a double-screw extruder for mixing, and performing melt extrusion, wire drawing, water cooling, air drying and granulating to prepare the flame-retardant composite material for the high-toughness battery outer cover.
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