CN114524990B - Wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material and preparation method and application thereof - Google Patents
Wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material and preparation method and application thereof Download PDFInfo
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 115
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 112
- -1 polypropylene Polymers 0.000 title claims abstract description 102
- 239000003792 electrolyte Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000002253 acid Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 41
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 41
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000010445 mica Substances 0.000 claims abstract description 14
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000454 talc Substances 0.000 claims description 10
- 229910052623 talc Inorganic materials 0.000 claims description 10
- 235000012222 talc Nutrition 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 30
- 239000000654 additive Substances 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
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- 239000002245 particle Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
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- 102100026887 Beta-defensin 103 Human genes 0.000 description 1
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- 101000912247 Homo sapiens Beta-defensin 103 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 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 description 1
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- 239000002184 metal Substances 0.000 description 1
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- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material, and a preparation method and application thereof. The polypropylene composite material comprises the following components in parts by weight: 60-75 parts of PP resin, 15-40 parts of flaky inorganic filler, 3-5 parts of compatilizer, 0.2-1 part of hyperbranched polymer and 0-1 part of other additives, wherein the flaky inorganic filler is talcum powder with a lamellar index of more than or equal to 2 and/or mica powder with a radial thickness ratio of more than or equal to 80; the branched chain end of the hyperbranched polymer is hydroxyl, and the number average molecular weight is 2500-3000 g/mol. The polypropylene composite material of the invention maintains a low linear expansion coefficient (< 110 mu m/(m.cndot.C.) within a wider temperature range (-30-80 ℃), and after being soaked in a flow battery electrolyte for 1000 hours at 70 ℃, the retention rate of the tensile strength of the material is more than 90 percent and can reach 98.2 percent.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material, and a preparation method and application thereof.
Background
With the rapid development of human economy and society, energy and environmental problems are also accompanied. In recent years, energy and environmental problems are also receiving more and more attention from the international society. However, a significant portion of clean energy sources have instability that requires integration with energy storage devices to be incorporated into the power grid. The flow battery is used as a novel electric storage and energy storage device, can be used for energy storage in the solar energy and wind energy power generation process, can be used for power grid peak shaving, and improves the stability of a power grid.
The flow battery realizes the conversion of electric energy and chemical energy through the reversible oxidation-reduction reaction of the positive and negative electrolyte, and the electrolyte directly flows in the plate-frame flow channel, so that the frame body material needs extremely excellent electrolyte resistance to ensure higher energy density in the use process of the battery; meanwhile, larger heat change and larger temperature difference change of external environment are easy to occur in the process of redox reaction of battery charge and discharge (for example, the temperature difference range is large in summer and winter in north China, the temperature is between minus 30 ℃ and 40 ℃), so that the frame material of the battery is required to have low linear expansion coefficient, and the phenomenon of liquid leakage caused by overlarge size change in the temperature change process is prevented.
Polypropylene (PP) has the advantages of good mechanical property, easy molding and processing, low cost and the like, and is one of four general materials. The polypropylene resin is a semi-crystalline thermoplastic plastic, has higher impact resistance, strong mechanical property, excellent performances of resisting various organic solvents, acid-base corrosion and the like, has good electrical property and high-frequency insulation, and can be widely applied to the fields of automotive interiors and batteries. However, when the modified polypropylene is applied to a flow battery, the common polypropylene material cannot meet the requirement of low shrinkage deformation in a wide temperature range, and the existing filling modified polypropylene cannot meet the requirement of maintaining the high energy efficiency of the flow battery in direct contact with strong acid electrolyte, so that the polypropylene needs to be modified to improve the electrolyte resistance and the low heat shrinkage performance of the polypropylene.
In the prior modification, the linear expansion coefficient of polypropylene is generally reduced by adding inorganic fillers such as talcum powder, wollastonite (such as a low linear expansion coefficient polypropylene compound and a preparation method thereof) and the like; the electrolyte resistance of polypropylene is improved by adding a sheet inorganic filler (such as a low-temperature super-tough electrolyte-resistant polypropylene modified material and a preparation method thereof), but no polypropylene material with low linear expansion coefficient and high electrolyte resistance is reported, the temperature range of the existing polypropylene material which can be kept at the low linear expansion coefficient and high electrolyte resistance is narrow, and different modified polypropylene materials are required to be selected respectively in different temperature environments, so that the manufacturing research and development cost is increased.
Therefore, there is a need to develop a polypropylene composite material that can be used over a larger temperature differential range while having a low linear expansion coefficient and high resistance to strong acid electrolytes.
Disclosure of Invention
The invention aims to fill the blank that the polypropylene material with low linear expansion coefficient and electrolyte resistance is not found, and further widens the use temperature range of the polypropylene material, so that the polypropylene material has low linear expansion coefficient and strong acid electrolyte resistance in a wider temperature range, and provides the wide-temperature-range low-shrinkage strong acid electrolyte-resistant polypropylene composite material.
The invention further aims at providing a preparation method of the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material.
The invention further aims to provide an application of the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material in preparation of a flow battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material comprises the following components in parts by weight:
wherein, the flaky inorganic filler is talcum powder with a lamellar index more than or equal to 2 and/or mica powder with a radial thickness ratio more than or equal to 80; the branched chain end of the hyperbranched polymer is hydroxyl, and the number average molecular weight is 2500-3000 g/mol.
The number average molecular weight of the hyperbranched polymer according to the invention was measured by GPC.
In the invention, a thinner flaky inorganic filler is selected, and the flaky inorganic filler is added, so that on one hand, the flaky inorganic filler can be orderly arranged along with the flow direction of polypropylene melt in the processing process, the barrier property of the material is improved, and the electrolyte is prevented from being infiltrated; on the other hand, the lamellar inorganic filler can also play a role of a nucleating agent in the polypropylene matrix, and further improve the crystallinity of the polypropylene resin matrix, thereby improving the rigidity of the polypropylene material. Under the combined action of the flaky inorganic filler and the relatively high crystalline polypropylene matrix, the strong acid electrolyte resistance of the polypropylene material can be obviously improved, and the linear expansion coefficient can be reduced.
In addition, if the heat resistance of the polypropylene material is to be widened, a large amount of flaky inorganic filler needs to be added, but the high-diameter-thickness ratio flaky inorganic filler has larger interfacial interaction force, so that the dispersibility of the flaky inorganic filler in a polypropylene resin matrix is poor, the phenomenon of aggregation easily occurs after a large amount of flaky inorganic filler is added, and the strong acid electrolyte resistance and the shrinkage resistance of the polypropylene material are further reduced. The inventors creatively found that, for example, the addition of a small amount of hyperbranched polymer having hydroxyl groups at the ends of the branched chains and being in a specific molecular weight range can significantly improve the dispersibility of the flaky inorganic filler in the crystalline polypropylene resin matrix, enabling the addition of a larger amount of flaky inorganic filler in the polypropylene resin matrix. The branched chain of the hyperbranched polymer can be firmly inserted into the polypropylene resin matrix, and the hydroxyl end of the branched chain has strong polarity, so that the branched chain can have strong interaction force with the polar group on the surface of the flaky inorganic filler, and the flaky inorganic filler is adsorbed to the tail end of the hyperbranched polymer, so that the flaky inorganic filler is uniformly dispersed in the polypropylene resin matrix.
Therefore, the invention is characterized in that the crystallinity of polypropylene is improved by adding thinner flaky inorganic filler (the larger the lamellar index of talcum powder is, the higher the thickness-diameter ratio of mica powder is, the thinner the filler is), and the strong acid electrolyte resistance and the linear expansion coefficient of the polypropylene material can be improved under the synergistic effect of the flaky inorganic filler and crystalline polypropylene; in addition, the addition of the specific hyperbranched polymer improves the addition amount of the ultrathin flaky inorganic filler, widens the heat resistance of the polypropylene material, and ensures that the polypropylene material has lower linear expansion coefficient and strong acid electrolyte resistance in a wider temperature range.
The inventor of the invention further discovers that if the molecular weight of the hyperbranched polymer is too small, the molecular weight of the hyperbranched resin is easy to be separated out, so that the strong acid electrolyte resistance of the polypropylene composite material is reduced; if the molecular weight of the hyperbranched resin is too large, the dispersibility of the hyperbranched resin in the polypropylene matrix is poor, and the interfacial property between the flaky inorganic filler and the polymer matrix cannot be effectively improved, so that the linear expansion coefficient and the strong acid electrolyte resistance of the polypropylene composite material are affected. Therefore, only the hyperbranched polymer having a molecular weight within the specific range selected in the present invention can improve the dispersibility of the flaky inorganic filler in the polypropylene resin matrix.
It should be noted that conventional commercially available PP (polypropylene) resins may be used in the present invention, alternatively, the PP resin may have a melt flow rate of 10 to 50g/10min at 230℃under a load of 2.16 kg.
In the invention, the melt flow rate of the PP resin is detected according to an ISO 1133-1:2011 standard method.
Preferably, the talc has a flake index of 3 to 6.
In the invention, the lamellar index of talcum powder is tested by using different particle size distribution testing methods: the D50 data of the laser particle sizer method and the sedimentation method are calculated according to the (D50 laser method-D50 sedimentation method)/D50 sedimentation method.
Preferably, the diameter-thickness ratio of the mica powder is 90-100.
Mica powder is generally in the form of a sheet, and the aspect ratio is a parameter describing the properties of mica powder in the art, which refers to the ratio of the diameter of the mica powder to its thickness.
In order to further improve the strong acid electrolyte resistance of the polypropylene composite material, the flaky inorganic filler can be also acid treated flaky inorganic filler, and the acid treatment can remove impurities which can react with the strong acid electrolyte in the flaky inorganic filler, so that the number of effective ions in the electrolyte is ensured, and the energy conversion efficiency in the charging and discharging processes of the battery is ensured.
Optionally, the acid is one or a combination of several of hydrochloric acid, sulfuric acid or nitric acid.
Optionally, the hyperbranched polymer (Hyperbranched Polymer, HBP for short) is a hydroxyl-terminated polyol.
Preferably, the crystallinity of the polypropylene in the polypropylene composite is 45-55%, the crystallinity being determined according to the method in GB/T19466.3-2004.
Optionally, the compatibilizer is polypropylene grafted maleic anhydride. It should be noted that conventional commercially available polypropylene grafted maleic anhydride may be used in the present invention.
It should be noted that the other additives include, but are not limited to, one or a combination of several antioxidants or lubricants.
Optionally, the antioxidant is one or a combination of more of hindered phenol antioxidants and/or phosphite antioxidants.
Optionally, the lubricant is one or a combination of a plurality of metal soap lubricant, stearic acid composite ester lubricant or amide lubricant.
Preferably, the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material comprises the following components in parts by weight:
the preparation method of the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material comprises the following steps:
uniformly mixing PP resin, flaky inorganic filler, compatilizer, hyperbranched polymer and processing aid according to a proportion, extruding at 190-220 ℃ and 450-600 rpm, and granulating.
Preferably, the mixing is performed in a high speed mixer with a frequency of 50Hz.
Preferably, the extrusion is performed in a twin screw extruder having an aspect ratio (L/D) of 48:1.
The application of the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material in preparing a flow battery is also within the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the crystallinity of the polypropylene is improved by adding the ultrathin flaky inorganic filler, and the flaky inorganic filler and the crystalline polypropylene cooperate to improve the rigidity of the polypropylene material; in addition, the addition of the specific hyperbranched polymer improves the addition amount of the ultrathin sheet inorganic filler, widens the heat-resistant temperature (the heat deformation temperature is more than 80 ℃) of the polypropylene material, ensures that the heat-resistant temperature is more than 80 ℃ within a wider temperature range (-30-80 ℃) and has a linear expansion coefficient of less than 110 mu m/(m DEG C), and the tensile strength retention rate of the material is more than 90 percent and can reach 98.2 percent after the polypropylene material is soaked in the electrolyte of a flow battery for 1000 hours at 70 ℃.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
The embodiment of the invention adopts the following raw materials:
PP resin:
PP-1: PP HC9012D, with a melt flow rate of 10g/10min at 230℃under a load of 2.16kg, was purchased from petrochemical Co., ltd. In Zhanjiang Dongxing, china;
PP-2: PP H9018, a melt flow rate of 50g/10min at 230℃under a 2.16kg load, available from Lanzhou petrochemical;
flake inorganic filler:
talcum powder-1: HTPULTra5L, lamellar index 2, purchased from Liaoning Aihaiyi Ore Co., ltd;
talcum powder-2: HAR 3g 77l, lamellar index 3, available from shanghai Hua Zhongrong industry, inc;
talcum powder-3: HAR T84, lamellar index 6, available from Shanghai Hua Zhongrong trade company, inc.;
talcum powder-4: AH-1250N6, lamellar index 1.5, available from Guangxi Shenghuamei Talc development Co., ltd;
mica powder-1: A-41S, having a ratio of 80, available from YAMAGUCHI;
mica powder-2: SYA-21RS, 90 gauge/thickness, available from YAMAGUCHI;
mica powder-3: b-82, having a ratio of 100, available from YAMAGUCHI;
mica powder-4: A-21S, having a ratio of about 70, available from YAMAGUCHI;
hyperbranched polymer:
HBP-1: hydroxyl-terminated polyol hyperbranched polymer, CYD-P214, with a number average molecular weight of 2500g/mol, purchased from Winhai morning source molecular new materials Co;
HBP-2: hydroxyl-terminated polyol hyperbranched polymer, CYD-P218, with a number average molecular weight of 3000g/mol, purchased from Wired morning source molecular new materials Co;
HBP-3: hydroxyl-terminated polyol hyperbranched polymer, HBP-158, having a number average molecular weight of 2800g/mol, available from WUHANZHUBrand resin technologies Co., ltd;
HBP-4: hydroxyl-terminated polyol hyperbranched polymer, hyperH 102, with a number average molecular weight of 1100g/mol, available from WUHan hyperbranched resin technologies Co., ltd;
HBP-5: hydroxyl-terminated polyol hyperbranched polymer, hyperH 104, having a number average molecular weight of 5400g/mol, available from WU-Han hyperbranched resin technologies Co., ltd;
HBP-6: the epoxy-terminated hyperbranched polymer, hyperE 102, has a number average molecular weight of 3000g/mol and is purchased from the chemical Co., ltd;
and (3) a compatilizer:
MAH-g-PP: PC-3, available from Nanhai Bo Chen polymeric New Material Co., ltd;
other additives:
hindered phenolic antioxidant 1010: are commercially available;
phosphite antioxidant 168: are commercially available;
amide type lubricants: ethylene bis stearamide, commercially available;
in the present invention, other additives were used in the same manner in each of examples and comparative examples.
Examples 1 to 13
The embodiment provides a series of wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite materials, which are prepared according to the formula in tables 1-2 and the preparation method comprises the following steps:
adding PP resin, flaky inorganic filler, compatilizer, hyperbranched polymer and processing aid into a high-speed mixer according to the proportion shown in tables 1-2, mixing for 5min, wherein the frequency of the high-speed mixer is 50Hz, and uniformly mixing to obtain a mixture; then adding the mixture into a double-screw extruder (the length-diameter ratio of the screw is L/D=48:1), and carrying out melt extrusion and granulation at the rotation speed of 450-600 rpm at the temperature of 190-220 ℃ (the temperature of the double-screw extruder from a feeding section to ten areas of a machine head is 190 ℃, 200 ℃, 205 ℃, 210 ℃, 220 ℃, 210 ℃, 205 ℃).
TABLE 1 Wide temperature Range Low shrinkage, strong acid resistant electrolyte Polypropylene composite materials of examples 1-5 (parts by weight)
TABLE 2 Wide temperature Range Low shrinkage, strong acid resistant electrolyte Polypropylene composite of examples 6-13 content (parts by weight) of each component
Note that: in the table, "1 x" represents talc-1 after acid treatment, which comprises the following specific steps: immersing talcum powder-1 in 2mol/L hydrochloric acid for reaction until the content of free elements in the supernatant (the content of free elements in the supernatant is obtained by carrying out total element detection and measurement by an ICP-AES method) is lower than 100ppm, filtering, collecting talcum powder precipitate, washing with clear water and drying.
Comparative example 1
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that talc is replaced with talc-4 having a flake index < 2.
Comparative example 2
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that talc is replaced with mica powder-4 having a ratio of radial to thickness of < 80.
Comparative example 3
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that the hyperbranched polymer is replaced by HBP-4 having a small number average molecular weight.
Comparative example 4
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that the hyperbranched polymer is replaced by HBP-5 having a large number average molecular weight.
Comparative example 5
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that the hyperbranched polymer is replaced with an epoxy-terminated hyperbranched polymer HBP-6.
Comparative example 6
This comparative example provides a polypropylene composite, the formulation differs from example 2 in that no hyperbranched polymer is added.
Performance testing
The polypropylene composite materials prepared in the above examples and comparative examples are injection molded to obtain corresponding test bars, and the performance thereof is tested, and specific test items and methods are as follows:
1. crystallinity: according to GB/T19466.3-2004;
2. linear expansion coefficient: the linear expansion coefficient of the polypropylene composite material in the range of minus 30 ℃ to 80 ℃ is tested by referring to the method in GB/T1036-1989 standard, and the maximum linear expansion coefficient is recorded;
3. heat distortion temperature: the test was carried out according to GB/T1634.2-2004 under the following conditions: the load is 1.8MPa, and the steel is horizontally placed;
4. tensile strength: the polypropylene composite material sample is soaked into a strong acid electrolyte (2 mol/L hydrochloric acid solution) with the temperature of 70 ℃ for 1000 hours, and the tensile strength of the polypropylene composite material before and after soaking in the electrolyte is tested according to GB/T1040.2-2006.
The test results are shown in Table 3.
TABLE 3 Performance test results
。
As can be seen from table 3:
in the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material prepared in each embodiment of the invention, the crystallinity of polypropylene is higher than 45 percent and can reach 52.4 percent; the linear expansion coefficient is less than 110 μm/(m.cndot.C) in the temperature range of-30-80 ℃ and can be as low as 98.5 μm/(m.cndot.C); after being soaked in hydrochloric acid electrolyte for 1000 hours at 70 ℃, the retention rate of the tensile strength of the material is more than 90 percent and can reach 98.2 percent (example 11), which shows that the material has good strong acid electrolyte resistance.
The results of example 2 and example 4 show that the PP resin matrix in the melt finger range selected by the invention can be used in the invention, and the prepared polypropylene composite material has lower linear expansion coefficient and excellent strong acid electrolyte resistance.
The results of examples 2, examples 6-11 and comparative examples 1-2 show that the ultrathin flaky inorganic filler selected by the invention can improve the crystallinity of polypropylene, further improve the rigidity of the polypropylene composite material, and further improve the strong acid electrolyte resistance and the low linear expansion coefficient in a wider temperature range of the polypropylene composite material. The sheet-like inorganic filler selected in comparative examples 1 and 2 was thicker, and in the polypropylene composite material prepared, the crystallinity of polypropylene was lower, and the rigidity was lowered, so that the electrolyte resistance performance was remarkably deteriorated.
The results of examples 2, 12-13 and comparative examples 3-4 show that the hyperbranched polymers with molecular weights within a specific range can significantly improve the compatibility between the flaky inorganic filler and the polypropylene resin matrix in the polypropylene composite material, further improve the dispersibility of the flaky inorganic filler in the polypropylene resin matrix and improve the performance of the polypropylene material. In the comparative example 3, hyperbranched polymer with smaller molecular weight is selected and soaked in electrolyte for 1000 hours, and precipitation phenomenon occurs; in comparative example 4, hyperbranched polymer with larger molecular weight is selected, and the dispersibility is poor, so that the strong acid electrolyte resistance of the prepared polypropylene composite material is obviously reduced.
In the comparative example 5, an epoxy group-terminated hyperbranched polymer is selected, and in the comparative example 6, no hyperbranched polymer is added, so that the strong acid electrolyte resistance of the prepared polypropylene composite material is obviously reduced.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material is characterized by comprising the following components in parts by weight:
wherein the flaky inorganic filler is talcum powder with a lamellar index of 2-6 and/or mica powder with a radial thickness ratio of 80-100; the hyperbranched polymer is hydroxyl-terminated polyol hyperbranched polymer, and the number average molecular weight is 2500-3000 g/mol; the crystallinity of polypropylene in the polypropylene composite material is 45-55%.
2. The broad temperature range low shrinkage strong acid resistant electrolyte polypropylene composite material according to claim 1, wherein the talc has a flake index of 3 to 6.
3. The wide temperature range low shrinkage and strong acid resistant electrolyte polypropylene composite material according to claim 1, wherein the mica powder has a radial thickness ratio of 90-100.
4. The wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material according to claim 1, wherein the flaky inorganic filler is an acid-treated flaky inorganic filler, and the acid is one or a combination of a plurality of hydrochloric acid or sulfuric acid.
5. The broad temperature range low shrinkage, strong acid resistant electrolyte polypropylene composite of claim 1, wherein the compatibilizer is polypropylene grafted maleic anhydride.
6. The wide temperature range low shrinkage strong acid resistant electrolyte polypropylene composite material according to claim 1, comprising the following components in parts by weight:
7. the method for preparing the wide-temperature-range low-shrinkage strong-acid-resistant electrolyte polypropylene composite material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
uniformly mixing PP resin, flaky inorganic filler, compatilizer, hyperbranched polymer and processing aid according to a proportion, extruding at 190-220 ℃ and 450-600 rpm, and granulating.
8. The use of the wide temperature range low shrinkage and strong acid resistant electrolyte polypropylene composite material of any one of claims 1-6 in the preparation of flow batteries.
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| PCT/CN2022/138883 WO2023155573A1 (en) | 2022-02-21 | 2022-12-14 | Broad-temperature-range, low-shrinkage, strongly-acidic-electrolyte-resistant polypropylene composite material, preparation method therefor and use thereof |
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