CN117844121A - Modified polypropylene material for storage battery shell, microcapsule used by modified polypropylene material and preparation method of microcapsule - Google Patents
Modified polypropylene material for storage battery shell, microcapsule used by modified polypropylene material and preparation method of microcapsule Download PDFInfo
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- CN117844121A CN117844121A CN202410098582.5A CN202410098582A CN117844121A CN 117844121 A CN117844121 A CN 117844121A CN 202410098582 A CN202410098582 A CN 202410098582A CN 117844121 A CN117844121 A CN 117844121A
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- microcapsule
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- silicone oil
- antioxidant
- polypropylene
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- -1 polypropylene Polymers 0.000 title claims abstract description 112
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 99
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 75
- 239000003094 microcapsule Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims description 6
- 238000003860 storage Methods 0.000 title description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003921 oil Substances 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 34
- 229920002545 silicone oil Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011257 shell material Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 28
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000011162 core material Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 239000004115 Sodium Silicate Substances 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 9
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 9
- 239000007764 o/w emulsion Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 2
- 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 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 238000000149 argon plasma sintering Methods 0.000 abstract description 6
- 238000002834 transmittance Methods 0.000 abstract description 5
- 239000001038 titanium pigment Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 235000010215 titanium dioxide Nutrition 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010586 diagram Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002569 water oil cream Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- WHFQAROQMWLMEY-UHFFFAOYSA-N propylene dimer Chemical compound CC=C.CC=C WHFQAROQMWLMEY-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
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
The formula of the modified polypropylene material comprises 93.7-98.1 parts of polypropylene resin, 0.3-0.8 part of diffusion oil, 0.5-2 parts of titanium pigment, 0.5-2.5 parts of microcapsule, 0.3-0.5 part of antioxidant and 0.3-0.5 part of lubricant; the grain diameter of the microcapsule is less than or equal to 300 mu m; the shell material of the microcapsule is silicon dioxide, and the core material is silicone oil; the refractive index of the silicone oil is consistent with that of the polypropylene resin. The addition of titanium dioxide enables the light transmittance of the polypropylene shell to be obviously reduced, thereby realizing the effect of reducing the effect of white knocking, and when the modified material is subjected to microcrack under the action of external force, the microcapsule at the position is also broken, the oily core material in the microcapsule is diffused and filled into the microcrack of the resin, and the selected oily material is close to the refractive index of the polypropylene resin, so that the light scattering degree of the position is reduced, the white knocking phenomenon on the surface of the battery shell is not obvious, and the effect of white knocking on the appearance of the battery is effectively reduced.
Description
Technical Field
The invention belongs to the field of storage batteries, and particularly relates to a modified polypropylene material for a storage battery shell.
Background
The shell of the lead-acid storage battery is generally made of a polypropylene copolymer material. Most of battery shells of storage batteries are of thin-wall structures, natural-color copolymerized polypropylene materials can be in a semitransparent state, the battery shells can be collided in the production and processing or carrying processes, under the condition, extremely small cracks (cracks invisible to naked eyes) are formed in the collided parts of the shells, light scattering is caused, the phenomenon of white knocking is shown, under the condition that electrolyte in the battery is reflected, the appearance of the battery is affected, the requirements of the appearance of the shells are difficult to meet, and the battery shells are easily identified as defective products by customers. For the whitening of the battery, no good solution exists in the industry, and a common practice is to add a buffer pad at the movement part of the processing equipment, which is in contact with the battery. However, this method can only reduce the occurrence probability of white knocking, and cannot fundamentally solve the white knocking phenomenon.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the modified polypropylene material for the storage battery shell, so that the influence of white-on-white on the appearance of the battery is effectively reduced.
The inventor researches and discovers that the cause of white knocking appears, after analysis, the following two points are found: 1. after the material is collided, tiny cracks appear, so that light scattering appears white; 2. the material is in a semi-permeable state, and the white knocking appears more obviously after the tank body is filled with electrolyte. If the problem is solved in the aspect of material modification, the problem of white knocking can be fundamentally solved by respectively coping with the two reasons. Aiming at the first point, when micro cracks appear in the material, if oily matter with refractive index close to that of the polypropylene material fills the cracks, the light scattering of the part is reduced, and then the white-off is not obvious; aiming at the second point, if inorganic pigment filler is added in the material, the light transmittance of the material is reduced, the light transmittance of the white-knocked part is close to that of the normal part, and the white-knocked phenomenon is not obvious. The influence of white knocking on the appearance can be reduced through the two points, and the white knocking problem is fundamentally solved.
The technical scheme adopted by the invention is as follows: the modified polypropylene material for the storage battery shell comprises the following raw materials in parts by weight:
93.7-98.1 parts of polypropylene resin,
0.3 to 0.8 part of diffusion oil,
0.5-2 parts of titanium dioxide,
0.5 to 2.5 parts of microcapsule,
0.3 to 0.5 part of antioxidant,
0.3-0.5 parts of lubricant;
the shell material of the microcapsule is silicon dioxide, and the core material is silicone oil;
the grain diameter of the microcapsule is less than or equal to 300 mu m.
Preferably, the formula comprises the following raw materials in parts by weight:
95.0 to 96.84 parts of polypropylene resin,
0.45-0.8 part of diffusion oil,
0.95-2 parts of titanium dioxide,
0.95-2.5 parts of microcapsule,
0.33 to 0.49 portion of antioxidant,
0.33-0.49 parts of lubricant.
The refractive index of the silicone oil is consistent with that of the polypropylene resin.
The polypropylene resin is a copolymerized polypropylene resin (typical brands are Yanshan petrochemical K8003, dushan petrochemical EPS30R, exxon mobil 7032KN and the like).
The diffusion oil is mineral oil (typically 10# white mineral oil, de-Carkii AK-1000, etc.).
The titanium dioxide is the rutile type titanium dioxide sold in the market, and the mesh number is 2400-5000.
The lubricant is ethylene bis stearamide, and the mesh number of the lubricant is 325-500 meshes.
The antioxidant is obtained by compounding a main antioxidant and an auxiliary antioxidant, and the compounding ratio of the antioxidant to the auxiliary antioxidant is 1:1.8-2.2 and uniformly mixing.
The main antioxidant is antioxidant 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester); the auxiliary antioxidant is antioxidant 168 (phosphite ester).
The preparation method of the modified polypropylene material for the storage battery shell comprises the following steps:
weighing polypropylene resin and diffusion oil according to the formula, and stirring for 1-2 minutes to uniformly mix the diffusion oil and the polypropylene resin to obtain polypropylene mixed with the diffusion oil;
weighing titanium dioxide, microcapsules, an antioxidant and a lubricant according to a formula, adding the titanium dioxide, the microcapsules, the antioxidant and the lubricant into the polypropylene mixed with the diffusion oil, stirring for 1-2 minutes to uniformly mix the components, and adhering the powder on the surfaces of polypropylene particles to form a blend;
the blend is put into a double-screw extruder, and the extrusion material strip is dried in water and pelletized at the temperature of 200-220 ℃ and the screw rotation speed of 350+ -10 rpm, the feeding frequency is 10+ -1 Hz, the vacuum degree is-0.1+ -0.01 MPa, and the anti-whitening modified polypropylene material can be obtained.
The microcapsule used in the modified polypropylene material comprises a core material and a coating shell outside the core material; the shell is silicon dioxide; the core material is silicone oil; the refractive index of the silicone oil is 1.50+/-0.1.
The silicone oil is phenyl methyl silicone oil or phenyl vinyl silicone oil, or other oily matter with refractive index of about 1.50.
The preparation method of the microcapsule comprises the following steps:
step one: adding a surfactant into the silicone oil, wherein the weight ratio of the surfactant to the silicone oil is 5% -10%; the silicone oil is phenyl methyl silicone oil or phenyl vinyl silicone oil; mixing the silicone oil mixture mixed with the surfactant with deionized water according to the weight ratio of 1:12.5-15, stirring the mixture at 60+ -5deg.C and 600+ -50 rpm for 20+ -5 min to form stable oil-in-water emulsion;
step two: weighing a proper amount of sodium silicate, adding deionized water with the same mass as the sodium silicate to prepare a sodium silicate solution, dropwise adding a hydrochloric acid solution with the concentration of 1+/-0.05 mol/L into the solution at the rotating speed of 600+/-50 rpm, adjusting the pH value of the solution to 3+/-0.2 so as to form a transparent silicic acid precursor solution, and continuously stirring for 30+/-5 minutes until the solution is stable;
step three: slowly dripping the silicic acid precursor solution obtained in the step II into the oil-in-water emulsion with the same mass as the silicic acid precursor solution, keeping the temperature of 60+/-5 ℃, and stirring for 24+/-0.5 hours at the rotating speed of 600+/-50 rpm; then, the stirring is closed, the temperature of 60+/-5 ℃ is kept unchanged, and the mixture is kept for 5+/-0.5 hours, so that the silicic acid precursor completes the polycondensation reaction on the surface of the silicon oil to generate a silicon dioxide shell, and a suspension of the microcapsule taking silicon dioxide as the shell and silicon oil as the core material is obtained;
step four: and standing the obtained suspension, separating, washing with deionized water, filtering to obtain a white product, and drying at 60+/-5 ℃ for 5+/-0.5 hours to obtain the microcapsule.
The surfactant is prepared by compounding dodecylphenol polyoxyethylene ether and cetyltrimethylammonium bromide, wherein the compounding ratio of the dodecylphenol polyoxyethylene ether to the cetyltrimethylammonium bromide is 1:1-1.5.
According to the invention, a certain amount of titanium dioxide is added, so that the light transmittance of the material is reduced under the condition that the appearance of the material is not changed; the microcapsule is added into the material, the microcapsule coats oily matters with refractive index close to that of the polypropylene material, when the shell is impacted, the microcapsule breaks to release the oily matters to fill micro cracks, and the light scattering of the part is reduced by the method, so that the effect of reducing the effect of white knocking is achieved.
The natural color polypropylene material is generally white, and titanium dioxide with the proportion of about 0.5-2% is added into the polypropylene material, so that the color of the polypropylene material is not greatly changed. However, on the one hand, the titanium dioxide has a stronger covering effect, and on the other hand, the addition of the titanium dioxide also changes the crystallization effect of the polypropylene material, and the two factors are overlapped, so that the light transmittance of the polypropylene shell is obviously reduced, and the effect of reducing the white impact is realized.
The invention adds the microcapsule with the mass ratio of about 0.5-2.5% into the polypropylene material, the shell material of the microcapsule is silicon dioxide, the core material is phenyl methyl silicone oil or phenyl vinyl silicone oil or other oily matters meeting the requirements, the refractive index of the polypropylene material is about 1.5, the refractive index of the selected oily matters is about 1.5, the two oily matters are close, in addition, the chemical property of the selected oily matters is stable, the heat resistance is good, and the performance of the battery is not affected by the addition of the selected oily matters into the polypropylene material. The processing gap of a common double-screw extruder is about 0.5mm, the size of the microcapsule prepared by the invention is not more than 300 mu m, and the shell material silicon dioxide has certain strength, so that the microcapsule cannot be broken in the processing process, and is uniformly dispersed in a resin matrix. When the modified material is subjected to microcracking under the action of external force, the microcapsules at the position are also simultaneously cracked, the oily core material in the microcapsules can be diffused and filled into the microcracks in the resin, and the selected oily material is close to the refractive index of the polypropylene resin, so that the light scattering degree of the position can be reduced, and the whitening phenomenon on the surface of the battery shell is not obvious.
Drawings
Fig. 1 is a state diagram before impact of an injection molding groove made of a modified polypropylene material for preventing white knocking in an embodiment of the invention.
Fig. 2 is a state diagram before impact of the injection molding groove body made of the modified polypropylene material with the anti-whitening effect according to the embodiment of the invention.
Fig. 3 is a state diagram before impact of an injection molding groove body made of the three-prevention white-knock-resistant modified polypropylene material in an embodiment of the invention.
FIG. 4 is a state diagram before impact of an injection molding tank body after adding titanium pigment to a common resin material of comparative example.
FIG. 5 is a state diagram before impact of a comparative example two-common resin injection molding tank.
Fig. 6 is a graph showing the effect of the anti-whitening modified polypropylene injection molding tank body according to the embodiment of the invention after impact.
Fig. 7 is a graph showing the effect of the second anti-whitening modified polypropylene material injection molding tank body after impact.
Fig. 8 is a graph showing the effect of the three-proofing white-gouging-prevention modified polypropylene material injection molding tank body after impact.
FIG. 9 shows the impact effect of the injection molding tank of the second comparative example.
FIG. 10 shows the effect of the injection molded cell body of the comparative example after impact.
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. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate.
Example 1
The method for synthesizing the microcapsule by using silicon dioxide as a shell and phenyl vinyl silicone oil as a core material through a sol-gel method comprises the following steps:
the first step: dodecyl phenol polyoxyethylene ether and hexadecyl trimethyl ammonium bromide are mixed according to the weight ratio of 2:3, compounding, stirring uniformly, and adding the mixture into phenyl vinyl silicone oil, wherein the adding proportion is 5% by mass; the phenyl vinyl silicone oil mixed with the surfactant and deionized water are mixed according to the weight ratio of 1:15, and stirring the mixture at 600rpm for 20 minutes at 60 ℃ to form a stable oil-in-water emulsion;
and a second step of: weighing a proper amount of sodium silicate, adding deionized water with the same mass to prepare a sodium silicate solution, dripping 1mol/L hydrochloric acid solution into the solution at the rotating speed of 600rpm, adjusting the pH value of the solution to 3 to form a transparent silicic acid precursor, and continuously stirring for 30 minutes until the solution is stable;
and a third step of: slowly dripping the silicic acid precursor solution into the oil-in-water emulsion, keeping the weight ratio of the added solution to be 1:1, keeping the temperature at 60 ℃, and stirring at 600rpm for 24 hours; then, the stirring is closed, the temperature of 60 ℃ is kept unchanged, and the mixture is kept for 5 hours, so that the silicic acid precursor completes the polycondensation reaction on the surface of the phenyl vinyl silicone oil to generate a silicon dioxide shell;
fourth step: and standing the obtained microcapsule suspension, separating, washing with deionized water, filtering to obtain a white product, and drying at 60 ℃ for 5 hours for later use.
10kg of polypropylene resin (commercially available copolymerized polypropylene, typical brand K8003) is weighed, 50g of diffusion oil is then weighed, and the diffusion oil and the polypropylene are uniformly mixed by stirring for 2 minutes; weighing 100g of titanium dioxide, 100g of self-made microcapsule, 36g of antioxidant (1010:168=1:2), 36g of lubricant, putting into the polypropylene mixed with the diffusion oil, stirring for 2 minutes, uniformly mixing the components, and sticking the powder on the surfaces of polypropylene particles; the blend is put into a double-screw extruder, and the extrusion material strip is dried in water and cut into particles at the feeding frequency of 10Hz and the vacuum degree of-0.1 MPa at the screw rotating speed of 350 revolutions per minute in the temperature range of 200-220 ℃ to obtain the anti-white modified polypropylene material.
The injection molding groove body made of the anti-white modified polypropylene material of the first embodiment is shown in figure 1.
Example two
The method for synthesizing the microcapsule by using silicon dioxide as a shell and phenyl methyl silicone oil as a core material through a sol-gel method comprises the following steps:
the first step: dodecyl phenol polyoxyethylene ether and hexadecyl trimethyl ammonium bromide are mixed according to the weight ratio of 1:1, after being compounded and stirred uniformly, the mixture is added into phenyl methyl silicone oil, wherein the adding proportion is 10% of the mass fraction; the phenyl methyl silicone oil mixed with the surfactant and deionized water are mixed according to the weight ratio of 2:25, and stirring the mixture at 600rpm for 20 minutes at 60 ℃ to form a stable oil-in-water emulsion;
and a second step of: weighing a proper amount of sodium silicate, adding deionized water with the same mass to prepare a sodium silicate solution, dripping 1mol/L hydrochloric acid solution into the solution at the rotating speed of 600rpm, adjusting the pH value of the solution to 3 to form a transparent silicic acid precursor, and continuously stirring for 30 minutes until the solution is stable;
and a third step of: slowly dripping the silicic acid precursor solution into the water-oil emulsion, keeping the weight ratio of the added solution to be 1:2, keeping the temperature at 60 ℃, and stirring at 600rpm for 24 hours; then, the stirring is closed, the temperature of 60 ℃ is kept unchanged, and the mixture is kept for 5 hours, so that the silicic acid precursor completes the polycondensation reaction on the surface of phenyl methyl silicone oil to generate a silicon dioxide shell;
fourth step: and standing the obtained microcapsule suspension, separating, washing with deionized water, filtering to obtain a white product, and drying at 60 ℃ for 5 hours for later use.
10kg of polypropylene resin (commercially available copolymerized polypropylene, typical brand EPS 30R) is weighed, 80g of white mineral oil is weighed, and the white mineral oil and the polypropylene are uniformly mixed by stirring for 2 minutes; 200g of titanium dioxide, 250g of self-made microcapsule, 36g of antioxidant (1010:168=1:2) and 36g of lubricant are weighed and put into the polypropylene mixed with the diffusion oil, and the mixture is stirred for 2 minutes, so that the components are uniformly mixed, and the powder is adhered to the surfaces of polypropylene particles; the blend is put into a double-screw extruder, and the extrusion material strip is dried in water and cut into particles at the feeding frequency of 10Hz and the vacuum degree of-0.1 MPa at the screw rotating speed of 350 revolutions per minute in the temperature range of 200-220 ℃ to obtain the anti-white modified polypropylene material.
The injection molding tank body made of the modified polypropylene material with the second anti-whitening effect is shown in fig. 2.
Example III
The method for synthesizing the microcapsule by using silicon dioxide as a shell and phenyl vinyl silicone oil as a core material through a sol-gel method comprises the following steps:
the first step: dodecyl phenol polyoxyethylene ether and hexadecyl trimethyl ammonium bromide are mixed according to the weight ratio of 1:1, after being compounded and stirred uniformly, the mixture is added into phenyl vinyl silicone oil, wherein the adding proportion is 8% of the mass fraction; the phenyl vinyl silicone oil mixed with the surfactant and deionized water are mixed according to the weight ratio of 1:15, and stirring the mixture at 600rpm for 20 minutes at 60 ℃ to form a stable oil-in-water emulsion;
and a second step of: weighing a proper amount of sodium silicate, adding deionized water with the same mass to prepare a sodium silicate solution, dripping 1mol/L hydrochloric acid solution into the solution at the rotating speed of 600rpm, adjusting the pH value of the solution to 3 to form a transparent silicic acid precursor, and continuously stirring for 30 minutes until the solution is stable;
and a third step of: slowly dripping the silicic acid precursor solution into the water-oil emulsion, keeping the weight ratio of the added solution to be 2:3, keeping the temperature at 60 ℃, and stirring at 600rpm for 24 hours; then, the stirring is closed, the temperature of 60 ℃ is kept unchanged, and the mixture is kept for 5 hours, so that the silicic acid precursor completes the polycondensation reaction on the surface of the phenyl vinyl silicone oil to generate a silicon dioxide shell;
fourth step: and standing the obtained microcapsule suspension, separating, washing with deionized water, filtering to obtain a white product, and drying at 60 ℃ for 5 hours for later use.
10kg of polypropylene resin (commercially available copolymerized polypropylene, typical brand EPS 30R) is weighed, 80g of diffusion oil is then weighed, and the diffusion oil and the polypropylene are uniformly mixed by stirring for 2 minutes; weighing 150g of titanium dioxide, 200g of self-made microcapsule, 50g of antioxidant (1010:168=1:2), 50g of lubricant, putting into the polypropylene mixed with the diffusion oil, stirring for 2 minutes, uniformly mixing the components, and adhering the powder on the surfaces of polypropylene particles; the blend is put into a double-screw extruder, the feeding frequency is 10Hz, the vacuum degree is-0.1 MPa, and the extruded material strip is dried in water and then cut into particles at the temperature range of 200-220 ℃ and the screw rotating speed of 350rpm, so that the anti-whitening modified polypropylene material can be obtained.
The injection molding tank body made of the modified polypropylene material with three anti-white collision properties is shown in fig. 3.
Comparative example one (titanium white powder added to common resin material)
10kg of polypropylene resin (commercially available copolymerized polypropylene, typical brand EPS 30R) is weighed, 80g of diffusion oil is then weighed, and the diffusion oil and the polypropylene are uniformly mixed by stirring for 2 minutes; weighing 150g of titanium dioxide, 50g of antioxidant (1010:168=1:2), adding 50g of lubricant into the polypropylene mixed with the diffusion oil, stirring for 2 minutes, and uniformly mixing the components to ensure that powder is adhered to the surfaces of polypropylene particles; the blend is put into a double-screw extruder, the feeding frequency is 10Hz, the vacuum degree is-0.1 MPa, and the extruded material strip is dried in water and pelletized at the temperature of 200-220 ℃ and the screw rotating speed of 350rpm, thus obtaining the polypropylene material.
The injection molded trough body from the comparative example-polypropylene material is shown in fig. 4.
Comparative example two (common resin Material)
10kg of polypropylene resin (commercially available copolymerized polypropylene, typical brand EPS 30R) is weighed, 80g of diffusion oil is then weighed, and the diffusion oil and the polypropylene are uniformly mixed by stirring for 2 minutes; weighing 50g of antioxidant (1010:168=1:2), adding 50g of lubricant into the polypropylene mixed with the diffusion oil, stirring for 2 minutes to uniformly mix the components, and sticking powder on the surfaces of polypropylene particles; the blend is put into a double-screw extruder, the feeding frequency is 10Hz, the vacuum degree is-0.1 MPa, and the extruded material strip is dried in water and pelletized at the temperature of 200-220 ℃ and the screw rotating speed of 350rpm, thus obtaining the polypropylene material.
The injection molded cell body from the comparative example propylene dimer material is shown in FIG. 5.
The battery jar is molded by the modified polypropylene materials with the anti-white effect, compared with the battery jar molded by the first (polypropylene material added with titanium white) and the battery jar molded by the second (common polypropylene material) of the comparative example, the white spots on the surface of the battery jar molded by the anti-white effect modified material are obviously better than those of the battery jar molded by the other two materials when the three battery jar sides are impacted by the 500g steel balls falling from the height of 55 cm. The anti-whitening modified polypropylene material prepared by the invention has good anti-whitening effect. The effect of the three material injection molded channel after impact is shown in figures 5-10.
The foregoing description of the exemplary embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A modified polypropylene material for a battery case, characterized by: the formula comprises the following raw materials in parts by weight:
93.7-98.1 parts of polypropylene resin,
0.3 to 0.8 part of diffusion oil,
0.5-2 parts of titanium dioxide,
0.5 to 2.5 parts of microcapsule,
0.3 to 0.5 part of antioxidant,
0.3-0.5 parts of lubricant;
the grain diameter of the microcapsule is less than or equal to 300 mu m;
the shell material of the microcapsule is silicon dioxide, and the core material is silicone oil.
2. The modified polypropylene material for battery cases according to claim 1, wherein: the formula comprises the following raw materials in parts by weight:
95.0 to 96.84 parts of polypropylene resin,
0.45-0.8 part of diffusion oil,
0.95-2 parts of titanium dioxide,
0.95-2.5 parts of microcapsule,
0.33 to 0.49 portion of antioxidant,
0.33-0.49 parts of lubricant.
3. The modified polypropylene material for battery cases according to claim 1, wherein: the refractive index of the silicone oil is consistent with that of the polypropylene resin.
4. The modified polypropylene material for battery cases according to claim 1, wherein: the polypropylene resin is copolymerized polypropylene resin; the diffusion oil is mineral oil; the titanium dioxide is commercial rutile type titanium dioxide, and the mesh number is 2400-5000 meshes; the lubricant is ethylene bis stearamide, and the mesh number of the lubricant is 325-500 meshes; the antioxidant is obtained by compounding a main antioxidant and an auxiliary antioxidant, and the compounding ratio of the antioxidant to the auxiliary antioxidant is 1:1.8-2.2.
5. The modified polypropylene material for battery cases according to claim 4, wherein: the main antioxidant is antioxidant 1010; the auxiliary antioxidant is antioxidant 168.
6. A process for the preparation of a modified polypropylene material for a battery casing as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
weighing polypropylene resin and diffusion oil according to the formula, and stirring for 1-2 minutes to uniformly mix the diffusion oil and the polypropylene resin to obtain polypropylene mixed with the diffusion oil;
weighing titanium dioxide, microcapsules, an antioxidant and a lubricant according to a formula, adding the titanium dioxide, the microcapsules, the antioxidant and the lubricant into the polypropylene mixed with the diffusion oil, stirring for 1-2 minutes to uniformly mix the components, and adhering the powder on the surfaces of polypropylene particles to form a blend;
the blend is put into a double-screw extruder, and the extrusion material strip is dried in water and pelletized at the temperature of 200-220 ℃ and the screw rotation speed of 350+ -10 rpm, the feeding frequency is 10+ -1 Hz, the vacuum degree is-0.1+ -0.01 MPa, and the anti-whitening modified polypropylene material can be obtained.
7. A microcapsule for use in the modified polypropylene material as claimed in any one of claims 1 to 5, characterized in that: comprises a core material and a cladding shell outside the core material; the shell is silicon dioxide; the core material is silicone oil; the refractive index of the silicone oil is 1.50+/-0.1.
8. Microcapsules according to claim 7, characterized in that: the silicone oil is phenyl methyl silicone oil or phenyl vinyl silicone oil.
9. A process for the preparation of microcapsules according to claim 7 or 8, characterized in that: the method comprises the following steps:
step one: adding a surfactant into the silicone oil, wherein the weight ratio of the surfactant to the silicone oil is 5% -10%; the silicone oil is phenyl methyl silicone oil or phenyl vinyl silicone oil; mixing the silicone oil mixture mixed with the surfactant with deionized water according to the weight ratio of 1:12.5-15, stirring the mixture at 60+ -5deg.C and 600+ -50 rpm for 20+ -5 min to form stable oil-in-water emulsion;
step two: weighing a proper amount of sodium silicate, adding deionized water with the same mass as the sodium silicate to prepare a sodium silicate solution, dropwise adding a hydrochloric acid solution with the concentration of 1+/-0.05 mol/L into the solution at the rotating speed of 600+/-50 rpm, adjusting the pH value of the solution to 3+/-0.2 so as to form a transparent silicic acid precursor solution, and continuously stirring for 30+/-5 minutes until the solution is stable;
step three: slowly dripping the silicic acid precursor solution obtained in the step II into the oil-in-water emulsion with the same mass as the silicic acid precursor solution, keeping the temperature of 60+/-5 ℃, and stirring for 24+/-0.5 hours at the rotating speed of 600+/-50 rpm; then, the stirring is closed, the temperature of 60+/-5 ℃ is kept unchanged, and the mixture is kept for 5+/-0.5 hours, so that the silicic acid precursor completes the polycondensation reaction on the surface of the silicon oil to generate a silicon dioxide shell, and a suspension of the microcapsule taking silicon dioxide as the shell and silicon oil as the core material is obtained;
step four: and standing the obtained suspension, separating, washing with deionized water, filtering to obtain a white product, and drying at 60+/-5 ℃ for 5+/-0.5 hours to obtain the microcapsule.
10. The method of preparing microcapsules according to claim 9, wherein: the surfactant is prepared by compounding dodecylphenol polyoxyethylene ether and cetyltrimethylammonium bromide, wherein the compounding ratio of the dodecylphenol polyoxyethylene ether to the cetyltrimethylammonium bromide is 1:1-1.5.
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