CN111592720A - Special polypropylene modified material for storage battery shell and preparation method thereof - Google Patents
Special polypropylene modified material for storage battery shell and preparation method thereof Download PDFInfo
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- CN111592720A CN111592720A CN201910411103.XA CN201910411103A CN111592720A CN 111592720 A CN111592720 A CN 111592720A CN 201910411103 A CN201910411103 A CN 201910411103A CN 111592720 A CN111592720 A CN 111592720A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 75
- -1 polypropylene Polymers 0.000 title claims abstract description 75
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000003860 storage Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000002667 nucleating agent Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000000806 elastomer Substances 0.000 claims abstract description 19
- 239000012764 mineral filler Substances 0.000 claims abstract description 13
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 21
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- 229920002943 EPDM rubber Polymers 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound 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 description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 238000011160 research Methods 0.000 claims description 4
- 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 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 241000218691 Cupressaceae Species 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A special polypropylene modified material for a storage battery shell and a preparation method thereof are disclosed, wherein polypropylene accounts for 70-90%; 5-20% of a toughening system; 3-10% of a reinforcing system; 0.5-1% of nucleating agent; 0.3-0.5% of antioxidant; 0.2-0.5% of lubricant. The method for preparing the one-step material by using the mineral filler and the polypropylene resin solves the problems of feeding bridging and uneven blanking caused by directly adding the superfine filler into a double-screw extruder and pollution caused by the fact that the superfine filler is easy to fly in the air, so that the filler is more uniformly dispersed in a polypropylene matrix, the whole manufacturing process is more environment-friendly, and the material has better mechanical property; the graft is selected as the toughening synergist, so that the compatibility of the filler and the polypropylene resin can be improved, and the dispersion of the elastomer in the polypropylene matrix is improved, so that the elastomer is more uniformly refined in the resin, and the ultralow-temperature impact performance is more excellent.
Description
Technical Field
The invention relates to a lead-acid storage battery polypropylene modified material, in particular to a polypropylene modified blending material for lead-acid storage battery shells matched with public automobiles, belonging to the field of lead-acid storage battery plastic modification.
Background
The mass automobile has extremely high market share in the Chinese market, and shows the strict manufacturing process and the extremely high technical level in Germany. Lead-acid storage battery shells used by mass automobiles also have high technical requirements, and the rigidity, toughness, normal temperature performance and high temperature performance of the materials are required to be optimal.
The polypropylene shell of the lead-acid battery required by the popular automobiles needs to meet the following performance requirements (part):
as can be seen from the above table, the technical requirements of the lead-acid storage battery case matched with the mass automobiles include low-temperature toughness (low-temperature ball drop impact), high temperature (2000 hours of aging), normal-temperature rigidity (normal-temperature stretching and normal-temperature bending), and chemical resistance (engine oil and grease resistance), and each requirement is independently used as an index and belongs to a high-level requirement; since rigidity and toughness are contradictory, the difficulty is great when putting together the various high level indicators.
Therefore, a polypropylene modified material needs to be designed, so that the performances in all aspects are balanced, the performances are comprehensively improved, and the requirements of lead-acid storage battery shells used by mass automobiles are met.
Disclosure of Invention
The invention aims to provide a special chemical corrosion resistant polypropylene modified material for a storage battery shell, which can meet the requirements of mass automobiles and has low-temperature toughness and normal-temperature rigidity.
The invention also aims to provide a preparation method of the special polypropylene modified material for the storage battery shell.
The technical scheme of the invention comprises the following components in parts by weight:
polypropylene: 70-90%;
a toughening system: 5-20%;
and (3) enhancing the system: 3-10%;
nucleating agent: 0.5-1%;
antioxidant: 0.3-0.5%;
lubricant: 0.2-0.5%;
other auxiliary agents: 0 to 0.4 percent;
the polypropylene is polypropylene resin;
the toughening system comprises an elastomer and a toughening synergist;
the reinforcing system is mineral filler.
The invention comprises the following components in optimal weight ratio:
polypropylene: 79 percent;
a toughening system: 12 percent;
and (3) enhancing the system: 8 percent;
nucleating agent: 0.4 percent;
antioxidant: 0.3 percent;
lubricant: 0.3 percent.
The isotacticity of the polypropylene resin is more than or equal to 90%, and the melt flow rate of the polypropylene resin is 1.5-3 g/10min at 230 ℃ under the condition of 2.16 kg; the polypropylene resin is K8003 of Yanshan petrochemical industry and 7032KN of Exxon Mobil. The polypropylene copolymer has high isotactic degree, high crystallization property and high rigidity, and after being compounded with a selected toughening system, the polypropylene composition has excellent impact resistance and high rigidity, and can simultaneously meet the requirements of public standards on rigidity and toughness. On the other hand, the polypropylene melt-finger interval is specially screened, so that the interval can meet the requirements of processing of the battery shell and subsequent battery assembly production, and can be used as a basic material of mass materials.
The toughening system of the invention is characterized in that the elastomer is one or a mixture of more of ethylene-propylene block copolymer, ethylene-propylene-diene monomer copolymer, polypropylene elastomer and ethylene-octene copolymer, the elastomer is ethylene-propylene-diene monomer rubber such as 3940 of Milliken, the polypropylene elastomer is NS06 of Mesughania, and POE is SK871 of Korea;
the toughening synergist is one or a mixture of more of polyethylene-maleic anhydride graft, polypropylene-maleic anhydride graft, polyethylene-glyceryl methacrylate graft and polypropylene-glyceryl methacrylate graft; the toughening synergist is commercially available as easy-to-use CMG9801, CMG5804, Nanhai cypress morning PC-1, etc.
The content of the toughening synergist in the toughening system is 5-20%. The addition of the toughening synergist can improve the dispersion effect of the elastomer, so that the polypropylene material has more excellent low-temperature impact resistance.
The reinforcing system is one or more of barium sulfate, diatomite and talcum powder as mineral fillers, wherein the barium sulfate is precipitated barium sulfate, the fineness of the barium sulfate is more than 5000 meshes, and the whiteness is better; the talcum powder is 5000 meshes-7000 meshes, and the diatomite is commercially available calcined diatomite with the fineness of more than 1000 meshes. SiliconThe diatomite is prepared by calcining at 750-plus 800 ℃ and processing through a multi-stage graded crushing process, and the integrity of the internal microporous structure can be ensured while the granularity is ensured. The talc powder is 5000 meshes-7000 meshes, the mineral filler mainly improves the rigidity, but not the traditional filling reduces the cost, on the other hand, the large cover and the small cover of the storage battery have the functions of acid resistance and exhaust, the structure is complex, more rib positions are included, if the traditional polypropylene material is used, the size and the performance of the product are influenced by the shrinkage, so that the mechanical property of the material can be improved by adding the proper filler, the size stability of the product can be improved, and the fineness of the screened mineral filler is far higher than that of the material with the common purpose; by controlling the composition and the adding proportion of the filler, the density of the final material is 0.91g/cm3The following.
The antioxidant of the invention is: the antioxidant is compounded by a main antioxidant and an auxiliary antioxidant; the main antioxidant is a general antioxidant 1010 and an antioxidant 1076 sold in the market, and the auxiliary antioxidant is an antioxidant DLTP or an antioxidant 168, wherein the weight ratio of the main antioxidant to the auxiliary antioxidant is 0.1-0.2 percent, and the weight ratio of the auxiliary antioxidant to the main antioxidant is 0.2-0.4 percent;
the nucleating agent is a beta nucleating agent, and the specific brands are a nucleating agent TMB-5 of Shanxi chemical research institute and a nucleating agent 3940 of Milliken;
the lubricant is a lubricant EBS, and the specific mark is a Yabao lubricant EBS 325-mesh, matchable and successful lubricant WAX 2006.
In addition, the composition also comprises the following other auxiliary components: weather resistant agent with the dosage of 0-0.3 percent of the total weight of the raw materials and pigment with the dosage of 0-1 percent of the total weight of the raw materials; the weather resistant agent is a general anti-ultraviolet absorbent sold in the market, the specific brands are UV-571 and UV-770, and the pigment is titanium dioxide.
The addition of the auxiliary agent meets the requirements of the product on processability, aging property, chemical stability and heat resistance.
The polypropylene modified material is used for producing the lead-acid storage battery shell, the storage battery shell belongs to a thin-wall product, and the minimum wall thickness is 1.8mm, so that good processing performance is ensured; there are differences in the color of the raw materials of different batches, so it is also necessary to add suitable pigments to control the color difference.
The preparation method of the polypropylene modified material for the lead-acid storage battery shell comprises the following steps:
1) the mineral filler and the polypropylene resin are added into a high-temperature mixing roll according to the proportion, premixed at the temperature of 170-210 ℃, granulated and cooled to obtain the primary material. The proportion range of the mineral filler and the polypropylene resin in the one-step material is 50-90%: 10 to 50 percent.
2) Uniformly mixing the above-mentioned one-step material with the rest of polypropylene resin, elastomer, toughening synergist, nucleating agent, antioxidant, lubricating agent and other adjuvant, adding them into double-screw extruder, melting and mixing at the temperature of 180-210 deg.C, then making water-passing, air-drying, granulating, drying, weighing and packaging. The length-diameter ratio of the double-screw extruder is 40: 1.
the high-temperature mixing machine is an internal mixer, a single-screw extruder or a double-screw extruder.
Compared with the prior art, the invention has the following beneficial effects: the method for preparing the one-step material by selecting the specific mineral filler and the polypropylene resin solves the problems of feeding bridging and uneven blanking caused by directly adding the superfine filler into a double-screw extruder and pollution caused by the superfine filler easily flying in the air, so that the filler is more uniformly dispersed in a polypropylene matrix, the whole manufacturing process is more environment-friendly, and the material has better mechanical property; the graft is selected as the toughening synergist in the formula system, so that the compatibility of the filler and the polypropylene resin can be improved on one hand, the dispersion of the elastomer in the polypropylene matrix is also improved on the other hand, the elastomer is more uniformly refined in the resin, and the ultralow-temperature impact performance is more excellent. Meanwhile, the selected polypropylene resin with proper melt index range and higher isotacticity is matched and used, so that the special material for the housing of the mass lead-acid storage battery prepared from the polypropylene material disclosed by the invention can meet the mass housing standard and pass related tests.
Detailed Description
The present invention will be described with reference to specific examples, but is not limited thereto.
Example 1
Firstly, 50 mass percent of polypropylene resin and 50 mass percent of precipitated barium sulfate are put into a high-temperature mixing roll, premixed at the temperature of 210 ℃, granulated and cooled to obtain a primary material; 16 mass percent of the above-mentioned one-step material, 71 mass percent of polypropylene resin, 10 mass percent of ethylene propylene diene monomer, 2 mass percent of maleic anhydride grafted polypropylene, 0.4 mass percent of nucleating agent, 0.1 mass percent of main antioxidant, 0.2 mass percent of auxiliary antioxidant and 0.3 mass percent of lubricant are mixed; adding the materials into a high-speed mixer, uniformly mixing, then putting the uniformly mixed materials into a double-screw extruder, carrying out melt mixing at the temperature of 190-210 ℃, then extruding, cooling, drying, weighing and packaging. The length to diameter ratio of the twin-screw extruder was 40.
The polypropylene resin is general polypropylene sold in the market, and the trade mark is K8003 copolymerized propylene of Dushan petrochemical industry, it is characterized in that the melt index range of the material is 1-3g/10min, the ethylene propylene diene monomer is a commercially available general material, and the grade is 4640 of DuPont, having a density of 0.86g/cm3, an ethylene content of 50% and a propylene content of 40%, the maleic anhydride graft being commercially available under the trade name CMG9801, the grafting rate is 1 percent, the nucleating agent is a general-purpose beta nucleating agent sold in the market, and the brand is as TMB-5 of Shanxi chemical research institute, the nucleating agent comprises sorbitol nucleating agent, main antioxidant 1010 of Yabao, auxiliary antioxidant 168 of Yabao, lubricant WAX2006 which can be successfully used, the mesh number of the lubricant is 325 mesh, and the above-mentioned raw material grade is only a specific description of the examples, as long as the object of the present invention is not limited.
Example 2
Firstly, 50% by mass of polypropylene resin, 25% by mass of talcum powder and 25% by mass of diatomite are put into a high-temperature mixing roll, premixed at the temperature of 210 ℃, granulated and cooled to obtain a primary material; mixing 12 mass percent of the above-mentioned primary raw material, 77 mass percent of polypropylene resin, 9 mass percent of ethylene propylene diene monomer, 1 mass percent of maleic anhydride grafted polypropylene, 0.2 mass percent of nucleating agent, 0.1 mass percent of main antioxidant, 0.2 mass percent of auxiliary antioxidant, 0.2 mass percent of lubricant and 0.3 mass percent of ultraviolet-resistant absorbent; adding the materials into a high-speed mixer, uniformly mixing, then putting the uniformly mixed materials into a double-screw extruder, carrying out melt mixing at the temperature of 190-210 ℃, then extruding, cooling, drying, weighing and packaging. The length to diameter ratio of the twin-screw extruder was 40.
The mineral filler selected by the formula is commercially available talcum powder and diatomite, wherein the mesh number of the talcum powder is 5000 meshes, the mesh number of the diatomite is 1000 meshes, the polypropylene resin is commercially available general-purpose polypropylene, the grade is as original petrochemical PPB-MH02 copolymerized propylene, and the polypropylene resin is characterized in that the melt index range of the material is 1-3g/10min, the ethylene propylene diene monomer rubber is commercially available general-purpose material, the grade is as 4640 of DuPont, the density is 0.86g/cm3, the ethylene content is 50%, the propylene content is 40%, the maleic anhydride graft is commercially available, the grade is as PC-1 of Nanhaibai, the grafting rate is 1%, the nucleating agent is as commercially available general-purpose beta nucleating agent, the grade is as 3940 of Milliken, the nucleating agent comprises sorbitol nucleating agent, the main antioxidant is as Yabao 1010, the auxiliary antioxidant is Yabao 168 lubricant is WAX2006 which can succeed, and the mesh number of the lubricant is 325 meshes, the weather resistant agent is a general-purpose ultraviolet resistant absorbent available on the market, and the trade name is UV-571, and the above raw material trade name is only used as a specific description of the embodiment, so long as the purpose of the invention is not limited.
Example 3
Firstly, 50 mass percent of polypropylene resin and 50 mass percent of precipitated barium sulfate are put into a high-temperature mixing roll, premixed at the temperature of 210 ℃, granulated and cooled to obtain a primary material; 20 mass percent of the above-mentioned one-step material, 64 mass percent of polypropylene resin, 12 mass percent of polypropylene elastomer, 2.5 mass percent of maleic anhydride grafted polypropylene, 0.3 mass percent of nucleating agent, 0.1 mass percent of main antioxidant, 0.3 mass percent of auxiliary antioxidant, 0.5 mass percent of lubricant and 0.3 mass percent of anti-ultraviolet absorbent are mixed; adding the materials into a high-speed mixer, uniformly mixing, then putting the uniformly mixed materials into a double-screw extruder, carrying out melt mixing at the temperature of 190-210 ℃, then extruding, cooling, drying, weighing and packaging. The length to diameter ratio of the twin-screw extruder was 40.
The polypropylene resin is general-purpose polypropylene sold in the market, the brand is K8003 copolymerized propylene of Du mountain petrochemical industry, and is characterized in that the melt index range of the material is 1-3g/10min, the ethylene propylene diene monomer is general-purpose material sold in the market, the brand is 4640 of DuPont, the density of the ethylene propylene rubber is 0.86g/cm3, the ethylene content is 50% and the propylene content is 40%, the maleic anhydride graft is sold in the market, the brand is CMG9801 which is good and easy to be obtained, the grafting rate of the CMG9801 is 1%, the nucleating agent is general-purpose beta nucleating agent sold in the market, the brand is TMB-5 of Shanxi chemical research institute, the nucleating agent comprises sorbitol nucleating agent, the main antioxidant is 1010 of Yabao, the auxiliary antioxidant is 168 of Yabao, the lubricant is WAX2006 which can be successfully sold in a race, the mesh number of the lubricant is 325 mesh, the weather-resistant agent is general-purpose light stabilizer sold in the market, the brand is UV-770, and the raw material brand is only taken as a concrete description, so long as it does not limit the object of the present invention.
Comparative example 1
Mixing polypropylene resin (82 wt%) such as Yanshan petrochemical K8003, polypropylene elastomer (10 wt%) such as Zhonghan petrochemical NS06, and talc (8 wt%) uniformly, adding into a twin-screw extruder, melting and mixing at 200 deg.C, granulating, cooling, drying, and packaging.
Results of Performance testing of the examples
The materials prepared in the above examples were injection molded to prepare test specimens in which (1) tensile strength: testing according to ISO 527 at a speed of 50 mm/min; (2) the density is carried out according to the method in GB/T1033; (3) the bending property test was carried out according to the method of GB/T9341. The deformation is set to be 10mm, the span is set to be 40mm, and the test speed is 14 mm/min;
from the product test result, the invention leads the comprehensive performance of the material to be optimal through the coordination of the toughening and stiffening system and the balance of the selection of the base material, and simultaneously meets the requirements of mass automobiles on the rigidity and the toughness of the lead-acid storage battery shell; the comparative example can not give consideration to rigidity and toughness, so that the material can not completely meet the requirements of mass automobiles.
Claims (9)
1. The special polypropylene modified material for the storage battery shell is characterized by comprising the following raw material components in parts by weight:
polypropylene: 70% -90%;
a toughening system: 5-20%;
and (3) enhancing the system: 3-10%;
nucleating agent: 0.5-1%;
antioxidant: 0.3-0.5%;
lubricant: 0.2-0.5%;
other auxiliary agents: 0 to 0.4 percent;
the polypropylene is polypropylene resin;
the toughening system comprises an elastomer and a toughening synergist;
the reinforcing system is mineral filler.
2. The special polypropylene modified material for the storage battery shell according to claim 1, which is characterized by comprising the following components in parts by weight:
polypropylene: 79 percent;
a toughening system: 12 percent;
and (3) enhancing the system: 8 percent;
nucleating agent: 0.4 percent;
antioxidant: 0.3 percent;
lubricant: 0.3 percent.
3. The polypropylene modified material special for the storage battery shell as claimed in claim 1, wherein: the isotacticity of the polypropylene resin is more than or equal to 90%, and the melt flow rate of the polypropylene resin is 1.5-3 g/10min at 230 ℃ under the condition of 2.16 kg; the polypropylene resin is K8003 of Yanshan petrochemical industry and 7032KN of Exxon Mobil.
4. The polypropylene modified material special for the storage battery shell as claimed in claim 1, wherein: the toughening system is characterized in that the elastomer is one or a mixture of more of ethylene-propylene block copolymer, ethylene-propylene-diene monomer copolymer, polypropylene elastomer and ethylene-octene copolymer, the elastomer is ethylene-propylene-diene monomer rubber such as 3940 of Milliken, the polypropylene elastomer is NS06 of Mesughania, and POE is SK871 of Korea;
the toughening synergist is one or more of polyethylene-maleic anhydride graft, polypropylene-maleic anhydride graft, polyethylene-glyceryl methacrylate graft and polypropylene-glyceryl methacrylate graft, such as CMG9801, CMG5804, and PC-1 in south China sea cypress;
the content of the toughening synergist in the toughening system is 5-20%.
5. The polypropylene modified material special for the storage battery shell as claimed in claim 1, wherein: the reinforcing system is one or more of barium sulfate, diatomite and talcum powder as mineral fillers, wherein the barium sulfate is precipitated barium sulfate, the fineness of the precipitated barium sulfate is more than 5000 meshes, the fineness of the talcum powder is 5000-7000 meshes, and the fineness of the diatomite is more than 1000 meshes.
6. The polypropylene modified material special for the storage battery shell as claimed in claim 1, wherein: the antioxidant is compounded by a main antioxidant and an auxiliary antioxidant; the main antioxidant is a general antioxidant 1010 and an antioxidant 1076 sold in the market, and the auxiliary antioxidant is an antioxidant DLTP or an antioxidant 168, wherein the weight ratio of the main antioxidant to the auxiliary antioxidant is 0.1-0.2 percent, and the weight ratio of the auxiliary antioxidant to the main antioxidant is 0.2-0.4 percent;
the nucleating agent is a beta nucleating agent, and the brands of the nucleating agent are TMB-5 of Shanxi chemical research institute and 3940 of Milliken;
the lubricant is EBS, and the grade is Yabao lubricant EBS325 mesh, Cuseif successful lubricant WAX 2006.
7. The special polypropylene modified material for the storage battery shell as claimed in claim 1, further comprising the following other auxiliary components: other auxiliary agents are weather resistant agents and pigments, the weather resistant agents are ultraviolet resistant absorbent UV-571 and light stabilizer UV-770, and the dosage of the weather resistant agents is 0.1-0.2% of the total weight of the raw materials; the pigment is titanium dioxide, and the dosage is 0-1% of the total weight of the raw materials.
8. The preparation method of the special polypropylene modified material for the storage battery shell as claimed in claim 1, characterized by comprising the following steps:
1) adding the mineral filler and the polypropylene resin into a high-temperature mixing roll in proportion, premixing at the temperature of 170-210 ℃, granulating and cooling to obtain a primary material; the weight ratio range of the mineral filler to the polypropylene resin in the one-step material is 50-90% to 10-50%;
2) uniformly mixing the above-mentioned first-step material with the rest of polypropylene resin, elastomer, toughening synergist, nucleating agent, antioxidant, lubricant and other auxiliary agents, adding them into double-screw extruder, melting and mixing at the temperature of 180-210 deg.C, then passing through water, air-drying, granulating, drying, weighing and packaging; the length-diameter ratio of the double-screw extruder is 40: 1.
9. the preparation method of the polypropylene modified material for the lead-acid storage battery shell according to claim 7, wherein the high-temperature mixing mill is an internal mixer, a single-screw extruder or a double-screw extruder.
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Application publication date: 20200828 |