CN116410542B - Modified polypropylene material for new energy automobile battery shell and preparation method thereof - Google Patents
Modified polypropylene material for new energy automobile battery shell and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 73
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 72
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 claims abstract description 43
- 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 claims abstract description 42
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 239000004611 light stabiliser Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 25
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 19
- 239000003365 glass fiber Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 41
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 33
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 33
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 150000003863 ammonium salts Chemical class 0.000 claims description 22
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 238000001694 spray drying Methods 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 16
- 229920001721 polyimide Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 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 group 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 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 8
- 238000009830 intercalation Methods 0.000 claims description 8
- 230000002687 intercalation Effects 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 239000002775 capsule Substances 0.000 claims description 7
- 239000011162 core material Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000004519 grease Substances 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 238000007725 thermal activation Methods 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 5
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 5
- 239000009719 polyimide resin Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011208 reinforced composite material 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000003466 welding Methods 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
- C08L23/12—Polypropene
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- 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)
Abstract
The invention discloses a modified polypropylene material for a new energy automobile battery shell and a preparation method thereof, wherein the modified polypropylene material comprises the following raw materials in parts by weight: 30-60 parts of polypropylene, 10-15 parts of polybutylene terephthalate, 15-20 parts of modified sericite, 10-12 parts of glass fiber, 5-8 parts of flame retardant, 5-10 parts of compatilizer, 0.5-2 parts of antioxidant, 0.1-1 part of light stabilizer and 1-3 parts of lubricant.
Description
Technical Field
The invention relates to the technical field of new energy automobiles, in particular to a modified polypropylene material for a battery shell of a new energy automobile and a preparation method thereof.
Background
Along with the development of science and technology and the improvement of people's environmental protection theory, people are increasingly focusing on the development and utilization of renewable energy sources, and new energy automobiles are one of hot spots. New energy automobiles are also beginning to be popular in people's lives. The new energy automobile adopts unconventional automobile fuel as power source, integrates advanced technology in the aspects of power control and driving of the automobile, and forms an automobile with advanced technical principle, new technology and new structure. The new energy automobiles comprise pure electric automobiles, extended range electric automobiles, hybrid electric automobiles, fuel cell electric automobiles, hydrogen engine automobiles, other new energy automobiles and the like, and the development potential is good.
The power battery is a core component of a new energy automobile and is generally arranged below a vehicle body bottom plate, and the battery assembly is fixedly connected to the vehicle body through a battery pack, so that the battery is more effective in use, the battery is better protected, the vehicle body is less affected, the battery pack needs to play roles in waterproof, fireproof and fixation, and the weight of the battery pack cannot be too heavy. Automobile weight reduction is an important requirement of new energy automobiles, and the weight reduction of battery shells of the new energy automobiles is also an important point and hot spot of research. The traditional battery pack is formed by welding steel or aluminum alloy materials, has heavy weight, is unfavorable for the light weight process of a new energy automobile, and is easy to have potential safety hazards; the other battery packs are lightweight material shells, and comprise glass fiber reinforced composite materials, SMC sheet materials, carbon fiber reinforced composite materials and the like, but the strength is low, and the mechanical requirements are not up to the standard.
The polypropylene material is the second largest plastic variety with the yield and the dosage which are inferior to those of polyethylene at present, has the advantages of light weight, good chemical resistance and high-frequency insulation performance, small specific gravity, easy processing and forming, low price and the like, and has wide application in the fields of automobile industry, electronic and electric industry, household appliances, textile and the like. The polypropylene material is used as the power battery shell to meet the requirement of light weight of the automobile, but the impact strength and flame retardant property of the polypropylene material cannot meet the requirement of the battery shell of the new energy automobile at present. Therefore, a high-strength and high-flame-retardant modified polypropylene material for a battery shell of a new energy automobile is needed to meet the requirements of effectively protecting a power battery from damage and spontaneous combustion when the automobile collides.
Disclosure of Invention
The invention aims to provide a modified polypropylene material for a new energy automobile battery shell and a preparation method thereof, wherein the flame retardant property of the material is effectively improved by adding polyimide coated modified ammonium polyphosphate flame retardant, the ageing resistance of the material is effectively improved by adding 2, 2-methylenebis (4-methyl-6-tert-butylphenol) intercalated modified sericite, and the mechanical property of the composite material is improved by adding a BS resin grafted glycidyl methacrylate-styrene copolymer compatilizer.
The aim of the invention can be achieved by the following technical scheme:
the modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 30-60 parts of polypropylene, 10-15 parts of polybutylene terephthalate, 15-20 parts of modified sericite, 10-12 parts of glass fiber, 5-8 parts of flame retardant, 5-10 parts of compatilizer, 0.5-2 parts of antioxidant, 0.1-1 part of light stabilizer and 1-3 parts of lubricant;
the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method;
the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol);
the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St).
The antioxidant is an antioxidant 1010 and an antioxidant P-EPQ according to a mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid complex grease or oleamide.
Further preferably, the preparation method of the flame retardant comprises the following steps:
(1) Dispersing ammonium polyphosphate and gamma-aminopropyl trimethoxy silane in absolute ethyl alcohol, heating to 90-100 ℃ for reaction for 3-5 hours, adding graphene oxide dispersion liquid into the solution, continuing to react for 3-5 hours to obtain gray black solid, washing with deionized water for 3-5 times, and freeze-drying to obtain modified ammonium polyphosphate;
(2) Adding the modified ammonium polyphosphate powder prepared in the step (1) into absolute ethyl alcohol to dissolve to obtain a solution A, dissolving polyimide resin powder into dimethylacetamide to obtain a solution B, mixing the two solutions, heating to 45-55 ℃, and stirring at constant temperature for 30-60min;
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 15-30min, and then carrying out spray drying to obtain the flame retardant.
Further preferably, in the step (1), the mass ratio of the ammonium polyphosphate, the gamma-aminopropyl trimethoxysilane and the graphene oxide is 30:2:1.
Further preferably, in step (2) the concentration of solution A is 0.16g/ml and the concentration of solution B is 0.2g/ml, the volume ratio of solution A to solution B being 2-3:1.
Further preferably, the spray drying in the step (3) is carried out at a feed rate of 15-18mL/min, an inlet air temperature of 80-90 ℃ and an outlet air temperature of 60-70 ℃.
Further preferably, the preparation method of the modified sericite comprises the following steps:
A. placing sericite in a muffle furnace, firstly heating to 180-220 ℃ at a speed of 5 ℃/min, then heating to 800-850 ℃ at a speed of 10 ℃/min, and calcining for 1-3h to obtain activated sericite;
B. adding activated sericite into nitric acid with the concentration of 8-12mol/L according to the solid-to-liquid ratio of 2-4%, stirring and reacting for 3-5 hours at the temperature of 90-95 ℃, and filtering and washing for several times to obtain acidified sericite;
C. adding the acidified sericite into a saturated sodium chloride solution according to a solid-to-liquid ratio of 2-4%, stirring and reacting for 3-5 hours at 90-95 ℃, and filtering and washing for several times to obtain the sodium sericite;
D. dissolving 2, 2-methylene bis (4-methyl-6-tertiary butyl phenol) in acetone, adding sodium sericite into 2, 2-methylene bis (4-methyl-6-tertiary butyl phenol) solution, performing ultrasonic treatment at 85-90 ℃ for 30-90min, and performing suction filtration and washing for several times to obtain the modified sericite.
Further preferably, the concentration of the 2,2 methylenebis (4-methyl-6-t-butylphenol) solution in the step D is 1.2g/ml, and the solid-to-liquid ratio of the sodium sericite to the 2,2 methylenebis (4-methyl-6-t-butylphenol) solution is 1:20-30.
Further preferably, the preparation method of the compatilizer comprises the following steps:
a. weighing ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide according to the proportion;
b. adding ABS resin and dicumyl peroxide into a mixing mill at 215-225 ℃ for melt mixing for 3-5min, adding glycidyl methacrylate and styrene, and continuing mixing for 3-5min;
c. the blend is rapidly sheared into small pieces, and then crushed by a crusher to obtain the small granular compatilizer.
Further preferably, the mass ratio of ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide in step a is 100:3:3:0.03.
The preparation method of the modified polypropylene material for the battery shell of the new energy automobile is characterized by comprising the following steps of:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a mixing mill at 215-225 ℃ for melt mixing for 5-10min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 5-10min;
s2, extruding the blend by a double screw extruder, wherein the temperatures of all areas of the extruder are 205-210 ℃, 225-230 ℃, 230-235 ℃, 235-240 ℃ and 240-245 ℃, and granulating the extruded material strips by a granulator after water cooling to obtain the modified polypropylene material.
The invention has the beneficial effects that:
according to the invention, the polyimide is used for coating the modified ammonium polyphosphate, so that the compatibility of the modified ammonium polyphosphate and the polypropylene is improved, meanwhile, the ionization energy of hydroxyl groups and carboxyl groups on the surface of the graphene oxide is utilized to form strong electrostatic interaction with the ammonium polyphosphate, meanwhile, the graphene oxide and the polypropylene have strong interfacial adhesion, and the modified ammonium polyphosphate can form a carbon layer in the combustion process to inhibit volatile matters from diffusing into flame, so that polymer chains are effectively protected, and the influence of oxygen and heat is reduced.
According to the invention, the sericite is subjected to heat activation, acidification and sodium treatment, so that the sericite sheet activity is improved, and then the activated sericite is subjected to intercalation modification by adopting 2, 2-methylenebis (4-methyl-6-tertiary butyl phenol), so that the intercalated modified sericite is prepared, and is added into a modified polypropylene material, so that the ageing resistance of the material is effectively improved.
According to the invention, the ABS resin is grafted with the glycidyl methacrylate-styrene copolymer as a compatilizer, styrene with the mass ratio of glycidyl methacrylate is added in the grafting process, so that the relative grafting degree can be effectively improved, the crosslinking degree is reduced, the impact strength of the PBT/PP composite material is increased, meanwhile, the particle size of a disperse phase is reduced due to the addition of ABS-g- (GMA-co-St), the compatibility of the composite material is improved, and the mechanical property of the polybutylene terephthalate/polypropylene composite material is improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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 modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 30 parts of polypropylene, 10 parts of polybutylene terephthalate, 15 parts of modified sericite, 10 parts of glass fiber, 5 parts of flame retardant, 5 parts of compatilizer, 0.5 part of antioxidant, 0.1 part of light stabilizer and 1 part of lubricant; the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method; the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol); the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St), and the antioxidant is antioxidant 1010 and antioxidant P-EPQ according to the mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is oleamide.
The preparation method of the flame retardant comprises the following steps:
(1) Dispersing ammonium polyphosphate and gamma-aminopropyl trimethoxy silane in absolute ethyl alcohol, heating to 92 ℃ for reaction for 3 hours, adding graphene oxide dispersion liquid into the solution, continuing the reaction for 3 hours to obtain gray black solid, washing 3-5 times with deionized water, and then freeze-drying to obtain modified ammonium polyphosphate, wherein the mass ratio of the ammonium polyphosphate to the gamma-aminopropyl trimethoxy silane to the graphene oxide is 30:2:1;
(2) Adding the modified ammonium polyphosphate powder prepared in the step (1) into absolute ethyl alcohol to dissolve to obtain a solution A with the concentration of 0.16g/ml, dissolving polyimide resin powder into dimethylacetamide to obtain a solution B with the concentration of 0.2g/ml, mixing the two solutions according to the volume ratio of 2:1, heating to 45 ℃, and stirring at constant temperature for 30min;
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 15min, and then carrying out spray drying to obtain the flame retardant, wherein the feeding speed of spray drying is 15mL/min, the air inlet temperature is 80 ℃, and the air outlet temperature is 60 ℃.
The preparation method of the modified sericite comprises the following steps:
A. placing sericite into a muffle furnace, firstly heating to 180 ℃ at a speed of 5 ℃/min, then heating to 800 ℃ at a speed of 10 ℃/min, and calcining for 1h to obtain activated sericite;
B. adding activated sericite into nitric acid with the concentration of 8mol/L according to the solid-to-liquid ratio of 2%, stirring and reacting for 3 hours at 90 ℃, and filtering and washing for several times to obtain acidified sericite;
C. adding the acidified sericite into a sodium chloride saturated solution according to a solid-to-liquid ratio of 2%, stirring and reacting for 3 hours at 90 ℃, and carrying out suction filtration and washing for several times to obtain the sodium-modified sericite;
D. 2, 2-methylenebis (4-methyl-6-t-butylphenol) was dissolved in acetone at a concentration of 1.2g/ml of 2, 2-methylenebis (4-methyl-6-t-butylphenol), and then sodium sericite was added at a solid-to-liquid ratio of 1:20 adding 2,2 methylene bis (4-methyl-6-tertiary butyl phenol) solution, carrying out ultrasonic treatment at 85 ℃ for 30min, and carrying out suction filtration and washing for several times to obtain the modified sericite.
The preparation method of the compatilizer comprises the following steps:
a. weighing ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide according to a mass ratio of 100:3:3:0.03;
b. adding ABS resin and dicumyl peroxide into a mixing mill at 215 ℃ for melt mixing for 3min, adding glycidyl methacrylate and styrene, and continuing mixing for 3min;
c. the blend is rapidly sheared into small pieces, and then crushed by a crusher to obtain the small granular compatilizer. The preparation method of the modified polypropylene material for the battery shell of the new energy automobile comprises the following steps:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a mixing mill at 215 ℃ to be mixed for 50 minutes in a melting way, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuing to mix for minutes;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 205 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Example 2
The modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 45 parts of polypropylene, 12 parts of polybutylene terephthalate, 18 parts of modified sericite, 10 parts of glass fiber, 6 parts of flame retardant, 8 parts of compatilizer, 1 part of antioxidant, 0.5 part of light stabilizer and 2 parts of lubricant; the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method; the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol); the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St), and the antioxidant is antioxidant 1010 and antioxidant P-EPQ according to the mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid composite grease.
The preparation method of the flame retardant comprises the following steps:
(1) Dispersing ammonium polyphosphate and gamma-aminopropyl trimethoxy silane in absolute ethyl alcohol, heating to 96 ℃ for reaction for 4 hours, adding graphene oxide dispersion liquid into the solution, continuing the reaction for 4 hours to obtain gray black solid, washing 3-5 times with deionized water, and then freeze-drying to obtain modified ammonium polyphosphate, wherein the mass ratio of the ammonium polyphosphate to the gamma-aminopropyl trimethoxy silane to the graphene oxide is 30:2:1;
(2) Adding the modified ammonium polyphosphate powder prepared in the step (1) into absolute ethyl alcohol to dissolve to obtain a solution A with the concentration of 0.16g/ml, dissolving polyimide resin powder into dimethylacetamide to obtain a solution B with the concentration of 0.2g/ml, mixing the two solutions according to the volume ratio of 3:1, heating to 50 ℃, and stirring at constant temperature for 45min;
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 20min, and then carrying out spray drying to obtain the flame retardant, wherein the feeding speed of spray drying is 16mL/min, the air inlet temperature is 85 ℃, and the air outlet temperature is 65 ℃.
The preparation method of the modified sericite comprises the following steps:
A. placing sericite into a muffle furnace, firstly heating to 200 ℃ at a speed of 5 ℃/min, then heating to 830 ℃ at a speed of 10 ℃/min, and calcining for 2 hours to obtain activated sericite;
B. adding activated sericite into nitric acid with the concentration of 10mol/L according to the solid-to-liquid ratio of 3%, stirring and reacting for 4 hours at 92 ℃, and filtering and washing for several times to obtain acidified sericite;
C. adding the acidified sericite into a sodium chloride saturated solution according to a solid-to-liquid ratio of 3%, stirring and reacting for 4 hours at 92 ℃, and carrying out suction filtration and washing for several times to obtain the sodium-modified sericite;
D. 2, 2-methylenebis (4-methyl-6-t-butylphenol) was dissolved in acetone at a concentration of 1.2g/ml of 2, 2-methylenebis (4-methyl-6-t-butylphenol), and then sodium sericite was added at a solid-to-liquid ratio of 1:25 adding 2,2 methylene bis (4-methyl-6-tertiary butyl phenol) solution, carrying out ultrasonic treatment at 88 ℃ for 60min, and carrying out suction filtration and washing for several times to obtain the modified sericite.
The preparation method of the compatilizer comprises the following steps:
a. weighing ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide according to the mass ratio of 100:3:3:0.0;
b. adding ABS resin and dicumyl peroxide into a mixing mill at 220 ℃ for melt mixing for 4min, adding glycidyl methacrylate and styrene, and continuously mixing for 4min;
c. the blend is rapidly sheared into small pieces, and then crushed by a crusher to obtain the small granular compatilizer. The preparation method of the modified polypropylene material for the battery shell of the new energy automobile comprises the following steps:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a 220 ℃ mixing mill for melt mixing for 8min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 8min;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 208 ℃, 228 ℃, 232 ℃, 237 ℃ and 243 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Example 3
The modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 58 parts of polypropylene, 15 parts of polybutylene terephthalate, 20 parts of modified sericite, 11 parts of glass fiber, 8 parts of flame retardant, 10 parts of compatilizer, 1.8 parts of antioxidant, 1 part of light stabilizer and 3 parts of lubricant; the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method; the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol); the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St). The antioxidant is an antioxidant 1010 and an antioxidant P-EPQ according to a mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid composite grease.
The preparation method of the flame retardant comprises the following steps:
(1) Dispersing ammonium polyphosphate and gamma-aminopropyl trimethoxy silane in absolute ethyl alcohol, heating to 98 ℃ for reaction for 5 hours, adding graphene oxide dispersion liquid into the solution, continuing the reaction for 5 hours to obtain gray black solid, washing 3-5 times with deionized water, and then freeze-drying to obtain modified ammonium polyphosphate, wherein the mass ratio of the ammonium polyphosphate to the gamma-aminopropyl trimethoxy silane to the graphene oxide is 30:2:1;
(2) Adding the modified ammonium polyphosphate powder prepared in the step (1) into absolute ethyl alcohol to dissolve to obtain a solution A with the concentration of 0.16g/ml, dissolving polyimide resin powder into dimethylacetamide to obtain a solution B with the concentration of 0.2g/ml, mixing the two solutions according to the volume ratio of 3:1, heating to 55 ℃, and stirring at constant temperature for 60min;
(3) And (3) carrying out ultrasonic treatment on the solution obtained in the step (2) for 30min, and then carrying out spray drying to obtain the flame retardant, wherein the feeding speed of spray drying is 18mL/min, the air inlet temperature is 90 ℃, and the air outlet temperature is 70 ℃.
The preparation method of the modified sericite comprises the following steps:
A. placing sericite into a muffle furnace, firstly heating to 220 ℃ at a speed of 5 ℃/min, then heating to 850 ℃ at a speed of 10 ℃/min, and calcining for 3 hours to obtain activated sericite;
B. adding activated sericite into nitric acid with the concentration of 12mol/L according to the solid-to-liquid ratio of 4%, stirring and reacting for 5 hours at 95 ℃, and filtering and washing for several times to obtain acidified sericite;
C. adding the acidified sericite into a sodium chloride saturated solution according to a solid-to-liquid ratio of 4%, stirring and reacting for 5 hours at 95 ℃, and carrying out suction filtration and washing for several times to obtain the sodium-modified sericite;
D. 2, 2-methylenebis (4-methyl-6-t-butylphenol) was dissolved in acetone at a concentration of 1.2g/ml of 2, 2-methylenebis (4-methyl-6-t-butylphenol), and then sodium sericite was added at a solid-to-liquid ratio of 1:30 adding 2,2 methylene bis (4-methyl-6-tertiary butyl phenol) solution, carrying out ultrasonic treatment at 90 ℃ for 90min, and carrying out suction filtration and washing for several times to obtain the modified sericite.
The preparation method of the compatilizer comprises the following steps:
a. weighing ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide according to a mass ratio of 100:3:3:0.03;
b. adding ABS resin and dicumyl peroxide into a mixer at 225 ℃ for melt mixing for 5min, adding glycidyl methacrylate and styrene, and continuing mixing for 5min;
c. the blend is rapidly sheared into small pieces, and then crushed by a crusher to obtain the small granular compatilizer. The preparation method of the modified polypropylene material for the battery shell of the new energy automobile comprises the following steps:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a 225 ℃ mixing mill for melt mixing for 10min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 10min;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 210 ℃, 230 ℃, 235 ℃, 240 ℃ and 245 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Comparative example 1
The modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 58 parts of polypropylene, 15 parts of polybutylene terephthalate, 11 parts of glass fiber, 8 parts of flame retardant, 10 parts of compatilizer, 1.8 parts of antioxidant, 1 part of light stabilizer and 3 parts of lubricant; the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method; the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St), and the antioxidant is antioxidant 1010 and antioxidant P-EPQ according to the mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid composite grease.
The preparation method of the flame retardant and the compatilizer is the same as that of the example 3.
The preparation method of the modified polypropylene material for the battery shell of the new energy automobile comprises the following steps:
s1, adding polypropylene, polybutylene terephthalate glass fiber and a compatilizer which are weighed according to a proportion into a 225 ℃ mixing mill for melt mixing for 10min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 10min;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 210 ℃, 230 ℃, 235 ℃, 240 ℃ and 245 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Comparative example 2
The modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 58 parts of polypropylene, 15 parts of polybutylene terephthalate, 20 parts of modified sericite, 11 parts of glass fiber, 10 parts of compatilizer, 1.8 parts of antioxidant, 1 part of light stabilizer and 3 parts of lubricant; the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol); the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St), and the antioxidant is antioxidant 1010 and antioxidant P-EPQ according to the mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid complex grease or oleamide.
The preparation method of the modified sericite and the compatilizer is the same as that of example 3.
The preparation method of the modified polypropylene material for the battery shell of the new energy automobile is characterized by comprising the following steps of:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a 225 ℃ mixing mill for melt mixing for 10min, adding an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 10min;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 210 ℃, 230 ℃, 235 ℃, 240 ℃ and 245 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Comparative example 3
The modified polypropylene material for the battery shell of the new energy automobile comprises the following raw materials in parts by weight: 58 parts of polypropylene, 15 parts of polybutylene terephthalate, 20 parts of modified sericite, 11 parts of glass fiber, 8 parts of flame retardant, 1.8 parts of antioxidant, 1 part of light stabilizer and 3 parts of lubricant; the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method; the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol); the antioxidant is an antioxidant 1010 and an antioxidant P-EPQ according to a mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid complex grease or oleamide.
The preparation method of the flame retardant and the modified sericite is the same as that of example 3.
The preparation method of the modified polypropylene material for the battery shell of the new energy automobile is characterized by comprising the following steps of:
s1, adding polypropylene, polybutylene terephthalate, modified sericite and glass fiber which are weighed according to a proportion into a 225 ℃ mixing mill for melt mixing for 10min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 10min;
s2, extruding the blend by a double-screw extruder, wherein the temperatures of all areas of the extruder are 210 ℃, 230 ℃, 235 ℃, 240 ℃ and 245 ℃, and granulating the extruded material strips by a granulator after water cooling, thus obtaining the modified polypropylene material.
Performance detection
1. Flame retardant Performance test
The modified polypropylene materials prepared in example 1-example 3, comparative example 1-comparative example 3 were processed into standard bars using a twin screw extruder, injection molding machine, and then the following tests were performed, respectively:
(1) vertical burn (UL-94) test
The test pieces were measured according to GB/T2408-2008 using a horizontal vertical combustion tester of model CZF-5, and the dimensions of the test pieces were 125 mm. Times.13 mm. Times.3 mm.
(2) Limiting oxygen index test
The spline size measured by the limiting oxygen index meter according to GB/T2406.2-2009 test standard was 80mm by 10mm by 4mm.
The flame retardant property test data are shown in table 1 below.
Table 1 flame retardant Property test results of modified Polypropylene materials
As can be seen from Table 1, in the modified polypropylene material, only the vertical burning grade in comparative example 2 is V-1, and the limiting oxygen index is smaller than that of other groups, and the data of other groups are equivalent, which shows that the polyimide coated modified ammonium polyphosphate flame retardant added by the invention effectively improves the flame retardant property of the composite material.
2. Aging resistance test
The modified polypropylene materials prepared in example 1-example 3 and comparative example 1-comparative example 3 were processed into standard bars by a twin screw extruder and an injection molding machine, and then subjected to a thermal oxidative aging test, concretely by subjecting the impact bars in the mechanical property test to an aging test of 7d,21d,35d at 140 c, and then testing the impact toughness of the bars according to the method in the notched impact strength test, to obtain the data shown in table 2 below.
TABLE 2 ageing resistance test results of modified Polypropylene materials
As can be seen from Table 2, in the modified polypropylene material, the mechanical property of the comparative example 1 is obviously reduced in the aging process at 140 ℃ for 35d compared with other groups, and the data of the other groups are equivalent, which shows that the composite material in the comparative example 1 has poor ageing resistance compared with the other groups, so that the ageing resistance of the material is effectively improved by adding the 2, 2-methylenebis (4-methyl-6-tert-butylphenol) intercalated modified sericite.
3. Mechanical property test
The modified polypropylene materials prepared in example 1-example 3, comparative example 1-comparative example 3 were processed into standard tensile bars and impact bars using a twin screw extruder, an injection molding machine, and then the following performance tests were performed, respectively:
(1) tensile Strength test
According to GB/T1040-1992, standard bars are subjected to tensile property test on an electronic universal tester, the tensile rate is selected to be 50mm/min, and the clamp spacing is 115mm.
(2) Notched impact strength test
The molded sheet was produced into a bar 80.+ -. 2mm long by 10.0.+ -. 0.2mm wide by 4mm thick according to GB/T1843-1996 standard. Preparing a V-shaped notch on a universal sampling machine, wherein the depth of the notch is 2mm; notched impact experiments were performed on a pendulum impact tester.
(3) Bending performance test
According to GB/T9341-2000 test, the compression rate is selected to be 2mm/min, and the clamp spacing is 64mm.
The mechanical properties test data obtained are shown in Table 3 below.
TABLE 3 mechanical Property test results of modified Polypropylene materials
As can be seen from Table 1, in the modified polypropylene material, the mechanical properties of comparative example 3 are significantly different from those of other groups, which indicates that the mechanical properties of the material are effectively improved by using the ABS resin grafted glycidyl methacrylate-styrene copolymer as a compatilizer, while the mechanical properties of comparative example 1 are slightly lower than those of other groups, probably because the modified sericite also has a certain influence on the mechanical properties of the material.
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 (9)
1. The modified polypropylene material for the battery shell of the new energy automobile is characterized by comprising the following raw materials in parts by weight: 30-60 parts of polypropylene, 10-15 parts of polybutylene terephthalate, 15-20 parts of modified sericite, 10-12 parts of glass fiber, 5-8 parts of flame retardant, 5-10 parts of compatilizer, 0.5-2 parts of antioxidant, 0.1-1 part of light stabilizer and 1-3 parts of lubricant;
the flame retardant is prepared by taking modified ammonium polyphosphate as a core material and polyimide as a capsule wall material through a low-temperature spray drying method;
the preparation method of the flame retardant comprises the following steps:
(1) Dispersing ammonium polyphosphate and gamma-aminopropyl trimethoxy silane in absolute ethyl alcohol, heating to 90-100 ℃ for reaction for 3-5 hours, adding graphene oxide dispersion liquid into the solution, continuing to react for 3-5 hours to obtain gray black solid, washing with deionized water for 3-5 times, and freeze-drying to obtain modified ammonium polyphosphate;
(2) Adding the modified ammonium polyphosphate powder prepared in the step (1) into absolute ethyl alcohol to dissolve to obtain a solution A, dissolving polyimide resin powder into dimethylacetamide to obtain a solution B, mixing the two solutions, heating to 45-55 ℃, and stirring at constant temperature for 30-60min;
(3) Carrying out ultrasonic treatment on the solution obtained in the step (2) for 15-30min, and then spray drying to obtain the flame retardant;
the modified sericite is obtained by thermal activation, acidification and sodium modification of sericite and then intercalation modification of 2, 2-methylenebis (4-methyl-6-tert-butylphenol);
the compatilizer is ABS resin grafted glycidyl methacrylate-styrene copolymer ABS-g- (GMA-co-St).
The antioxidant is an antioxidant 1010 and an antioxidant P-EPQ according to a mass ratio of 1:1, wherein the light stabilizer is an ultraviolet absorber UV-P, and the lubricant is stearic acid complex grease or oleamide.
2. The modified polypropylene material for the battery case of the new energy automobile according to claim 1, wherein the mass ratio of the ammonium polyphosphate, the gamma-aminopropyl trimethoxysilane and the graphene oxide in the step (1) is 30:2:1.
3. The modified polypropylene material for battery cases of new energy automobiles according to claim 1, wherein the concentration of the solution a in the step (2) is 0.16g/ml, the concentration of the solution B is 0.2g/ml, and the volume ratio of the solution a to the solution B is 2-3:1.
4. The modified polypropylene material for battery cases of new energy vehicles according to claim 1, wherein the spray-drying in the step (3) has a feed rate of 15-18mL/min, an inlet air temperature of 80-90 ℃ and an outlet air temperature of 60-70 ℃.
5. The modified polypropylene material for a battery case of a new energy automobile according to claim 1, wherein the preparation method of the modified sericite comprises the following steps:
A. placing sericite in a muffle furnace, firstly heating to 180-220 ℃ at a speed of 5 ℃/min, then heating to 800-850 ℃ at a speed of 10 ℃/min, and calcining for 1-3h to obtain activated sericite;
B. adding activated sericite into nitric acid with the concentration of 8-12mol/L according to the solid-to-liquid ratio of 2-4%, stirring and reacting for 3-5 hours at the temperature of 90-95 ℃, and filtering and washing for several times to obtain acidified sericite;
C. adding the acidified sericite into a saturated sodium chloride solution according to a solid-to-liquid ratio of 2-4%, stirring and reacting for 3-5 hours at 90-95 ℃, and filtering and washing for several times to obtain the sodium sericite;
D. dissolving 2, 2-methylene bis (4-methyl-6-tertiary butyl phenol) in acetone, adding sodium sericite into 2, 2-methylene bis (4-methyl-6-tertiary butyl phenol) solution, performing ultrasonic treatment at 85-90 ℃ for 30-90min, and performing suction filtration and washing for several times to obtain the modified sericite.
6. The modified polypropylene material for a battery case of a new energy automobile according to claim 5, wherein the concentration of the 2,2 methylenebis (4-methyl-6-t-butylphenol) solution in the step D is 1.2g/ml, and the solid-to-liquid ratio of the sodium sericite to the 2,2 methylenebis (4-methyl-6-t-butylphenol) solution is 1:20-30.
7. The modified polypropylene material for a battery case of a new energy automobile according to claim 1, wherein the preparation method of the compatibilizer comprises the steps of:
a. weighing ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide according to the proportion;
b. adding ABS resin and dicumyl peroxide into a mixing mill at 215-225 ℃ for melt mixing for 3-5min, adding glycidyl methacrylate and styrene, and continuing mixing for 3-5min;
c. the blend is rapidly sheared into small pieces, and then crushed by a crusher to obtain the small granular compatilizer.
8. The modified polypropylene material for a battery case of a new energy automobile according to claim 7, wherein the mass ratio of the ABS resin, glycidyl methacrylate, styrene and dicumyl peroxide in the step a is 100:3:3:0.03.
9. A method for preparing the modified polypropylene material for the battery case of the new energy automobile according to any one of claims 1 to 8, comprising the steps of:
s1, adding polypropylene, polybutylene terephthalate, modified sericite, glass fibers and a compatilizer which are weighed according to a proportion into a mixing mill at 215-225 ℃ for melt mixing for 5-10min, adding a flame retardant, an antioxidant, a light stabilizer and a lubricant, and continuously mixing for 5-10min;
s2, extruding the blend by a double screw extruder, wherein the temperatures of all areas of the extruder are 205-210 ℃, 225-230 ℃, 230-235 ℃, 235-240 ℃ and 240-245 ℃, and granulating the extruded material strips by a granulator after water cooling to obtain the modified polypropylene material.
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| CN115340828A (en) * | 2022-07-04 | 2022-11-15 | 江西昊泽光学膜科技有限公司 | Lithium ion battery termination adhesive tape with corrosion resistance |
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| CN102408524A (en) * | 2011-11-21 | 2012-04-11 | 福建师范大学 | Multi-monomer melt-grafted acrylonitrile-butadiene-styrene copolymer and preparation method thereof |
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