CN115490961A - Modified polypropylene material for refrigerator freezing drawer, preparation method of modified polypropylene material, refrigerator freezing drawer and refrigerator - Google Patents
Modified polypropylene material for refrigerator freezing drawer, preparation method of modified polypropylene material, refrigerator freezing drawer and refrigerator Download PDFInfo
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- CN115490961A CN115490961A CN202211253367.5A CN202211253367A CN115490961A CN 115490961 A CN115490961 A CN 115490961A CN 202211253367 A CN202211253367 A CN 202211253367A CN 115490961 A CN115490961 A CN 115490961A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 99
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 96
- -1 polypropylene Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 72
- 230000008014 freezing Effects 0.000 title claims abstract description 43
- 238000007710 freezing Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 98
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- 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 abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 12
- 230000003179 granulation Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910001422 barium ion Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 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 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical group CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 3
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 3
- 230000005012 migration Effects 0.000 abstract description 52
- 238000013508 migration Methods 0.000 abstract description 52
- 238000012360 testing method Methods 0.000 abstract description 36
- 235000013305 food Nutrition 0.000 abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 18
- 239000004033 plastic Substances 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 239000000945 filler Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D11/00—Self-contained movable devices, e.g. domestic refrigerators
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D25/00—Charging, supporting, and discharging the articles to be cooled
- F25D25/02—Charging, supporting, and discharging the articles to be cooled by shelves
- F25D25/024—Slidable shelves
- F25D25/025—Drawers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a modified polypropylene material for a refrigerator freezing drawer, a preparation method thereof and the refrigerator freezing drawer, belongs to the field of polypropylene composite materials, and can solve the problem that the existing modified polypropylene material cannot simultaneously meet food grade requirements specified by European Union plastic food contact materials and article regulations EU 10/2011 and national standard G B4806. The modified polypropylene material for the refrigerator freezing drawer comprises the following components in parts by mass: 65-70 parts of PP resin, 15-20 parts of barium sulfate, 15-20 parts of talcum powder, 1-5 parts of cold-resistant plasticizer, 0.1-1.5 parts of coupling agent, 1.5-2 parts of toughening agent, 0.5-2 parts of lubricant and 0.2-1.5 parts of antioxidant. The modified polypropylene material can be applied to refrigerator freezing drawers, and the drawer meeting the requirements of food contact regulations can reduce the possibility of cracking of the drawer at ultralow temperature through comprehensive migration and heavy metal special migration tests.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and particularly relates to a modified polypropylene material for a refrigerator freezing drawer, a preparation method of the modified polypropylene material and the refrigerator freezing drawer.
Background
Pure Polypropylene (PP) is a preferred plastic variety in the household appliance industry due to its low density, good chemical resistance, low price, excellent comprehensive properties, and the like.
Because the pure PP material has larger shrinkage, the pure PP material is applied to a common freezing drawer of a refrigerator and has the problems of easy deformation, poor impact strength, easy cracking and the like, and at present, the modified calcium carbonate is generally adopted to fill the PP material in the ice cooling industry to solve the problems; the temperature of a freezing chamber of a common refrigerator is usually not more than-30 ℃, but with the upgrading of consumption requirements, the drawer design of the freezing chamber of the refrigerator is possibly lower than-40 ℃ so as to meet the storage requirements of users for high-end seafood materials, but the existing refrigerator freezing drawer cannot meet the ultralow temperature use requirements and has the problem of easy low-temperature deformation, and the cryogenic drawer is usually manufactured by high-toughness modified ABS in the industry at present.
Calcium carbonate is filled in PP and applied to a refrigerator drawer, and as the calcium carbonate reacts with acetic acid, evaporation residues generated by the reaction exceed the limit value required by the regulations and can not meet the comprehensive migration tests of 3% acetic acid and 4% acetic acid required by EU 10/2011 and GB4806 standards of European Union plastic food contact materials and articles; the high-toughness modified ABS has higher price and low product profit, and the ABS material has monomer residues of acrylonitrile and butadiene, so that the special migration of acrylonitrile is unqualified in accordance with EU 10/2011 plastic regulations of European Union.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the modified polypropylene material which is ultralow in temperature and high in glossiness and meets food grade, the preparation method and the refrigerator freezing drawer, and the drawer meeting the requirements of food contact regulations reduces the possibility of cracking at ultralow temperature through comprehensive migration and heavy metal special migration tests.
In order to achieve the purpose, the invention adopts the technical scheme that: the modified polypropylene material for the refrigerator freezing drawer comprises the following components in parts by weight: 65-70 parts of PP resin, 15-20 parts of barium sulfate, 15-20 parts of talcum powder, 1-5 parts of cold-resistant plasticizer, 0.1-1.5 parts of coupling agent, 1.5-2 parts of toughening agent, 0.5-2 parts of lubricant and 0.2-1.5 parts of antioxidant, wherein the content of barium ions in the barium sulfate is lower than 10mg/kg, and the particle size range of the barium sulfate is 6250 meshes-8000 meshes; the particle size range of the talcum powder is 1000 meshes-1500 meshes.
In one embodiment, the barium sulfate is spherical barium sulfate produced by a precipitation method, and sulfuric acid is added again after the precipitation reaction is completed to remove free barium ions.
In one embodiment, the cold resistant plasticizer is at least one of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultrahigh molecular weight polyethylene.
In one embodiment, the coupling agent is at least one of an aluminate coupling agent, a silane coupling agent, and a titanate coupling agent.
In one embodiment, the toughening agent is at least one of polyolefin elastomer grafted maleic anhydride copolymer and ethylene propylene diene monomer grafted maleic anhydride copolymer.
In one embodiment, the lubricant is oleamide and the antioxidant is pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite at a ratio of 1: 1.
The invention also provides a preparation method of the modified polypropylene material for the refrigerator freezer drawer, which is characterized by comprising the following steps: respectively weighing PP resin, barium sulfate, cold-resistant plasticizer, coupling agent, toughening agent, lubricant, antioxidant and barium sulfate according to the set mass parts, putting the PP resin, the barium sulfate, the cold-resistant plasticizer, the coupling agent, the toughening agent, the lubricant, the antioxidant and the barium sulfate in a high-speed stirrer, and stirring for 10-30 minutes until all the components are uniformly mixed to obtain a mixture A;
weighing talcum powder according to the set mass portion, and uniformly stirring the talcum powder and the mixture A again for 10-15 minutes to obtain a final mixture B;
and starting the double-screw extruder, putting the mixture B into the double-screw extruder for extrusion granulation, carrying out melt blending, extrusion, cooling and granulation, fully melting and compounding the materials under the shearing, mixing and conveying of the screws, and carrying out extrusion granulation and drying to obtain the modified polypropylene material for the refrigerator freezing drawer.
In one embodiment, the temperature of the twin screw extruder is set to: the temperature of a pre-melting temperature zone is 140-160 ℃, the temperature of a first zone is 170-190 ℃, the temperature of a second zone is 190-220 ℃, the temperature of a third zone is 210-220 ℃, the temperature of a fourth zone is 200-220 ℃, and the temperature of a discharge port temperature zone is 190-200 ℃; the rotating speed of the screw is 300r/min-400r/min.
The invention provides a refrigerator freezing drawer, which is prepared from the modified polypropylene material for the refrigerator freezing drawer in any embodiment.
The invention provides a refrigerator, which comprises the refrigerator freezing drawer.
Compared with the prior art, the invention has the advantages and positive effects that:
(1) According to the invention, spherical barium sulfate and talcum powder are compounded to be used as a filling agent, wherein the content of barium ions of the barium sulfate is lower than 10mg/kg, the barium metal exceeding standard can be avoided, the high glossiness and whiteness of the product are improved, the talcum powder is added to replace part of barium sulfate, the cost is reduced, the high impact resistance and high strength structural performance of a PP material are realized after the spherical barium sulfate and the talcum powder are compounded, and the shrinkage rate of the product after molding is reduced; the toughness of the PP material is enhanced by the aid of the cold-resistant plasticizer, so that the toughness of the PP material under the ultralow-temperature condition can be met; and the mechanical property of the PP material is improved by adding the coupling agent.
(2) The addition sequence of the barium sulfate and the talcum powder in the steps of the preparation method of the modified polypropylene material for the refrigerator freezing drawer is different, and the bonding property and the dispersity of the filler and the matrix are improved and the compatibility is improved by improving the addition process of the two fillers.
(3) The refrigerator freezing drawer processed and produced by the modified polypropylene material for the refrigerator freezing drawer provided by the invention can meet the requirements of food contact regulations, and the drawer can reduce the possibility of cracking under the ultralow temperature condition below-40 ℃ through comprehensive migration and heavy metal special migration tests, and has high glossiness.
Detailed Description
In order to make the objects and embodiments of the present invention clearer, the following will clearly and completely describe exemplary embodiments of the present invention, and it is obvious that the described exemplary embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
It should be noted that the brief descriptions of the terms in the present application are only for convenience of understanding of the embodiments described below, and are not intended to limit the embodiments of the present application. These terms should be understood in their ordinary and customary meaning unless otherwise indicated.
The embodiment of the invention provides a modified polypropylene material for a refrigerator freezing drawer, a preparation method thereof and the refrigerator freezing drawer, wherein the modified polypropylene material for the refrigerator freezing drawer comprises the following raw materials in parts by weight: 65-70 parts of PP resin, 15-20 parts of barium sulfate, 15-20 parts of talcum powder, 1-5 parts of cold-resistant plasticizer, 0.1-1.5 parts of coupling agent, 1.5-2 parts of toughening agent, 0.5-2 parts of lubricant and 0.2-1.5 parts of antioxidant, wherein the barium sulfate is spherical barium sulfate produced by adopting a precipitation method, a process flow for removing barium ions is additionally added in the last step of the production process of the barium sulfate, and the specific operation is that the sulfuric acid is added again after the precipitation reaction is finished, so that the sulfuric acid and free barium ions are subjected to chemical reaction, and the purpose of collecting the free barium ions is achieved. By the method, the content of barium ions in the barium sulfate is controlled within 10mg/kg, and the prepared modified polypropylene material is soaked in isooctane, 95% ethanol and 3% or 4% acetic acid when a comprehensive migration test and a special heavy metal migration test of a food contact material are carried out, so that the migration condition cannot occur. The talcum powder disclosed by the invention is prepared from food-grade talcum powder, the main component of the talcum powder is silicon dioxide, the particle size range of the talcum powder is 1000-1500 meshes, the talcum powder has acid and alkali corrosion resistance, and in the overall migration and special migration tests, the talcum powder is soaked in isooctane, 95% ethanol and 3% or 4% acetic acid, so that the migration situation cannot occur. As the particle size of the barium sulfate is larger, the weather resistance and the glossiness are better, but the dispersity is poor, the particle size range of the spherical barium sulfate adopted by the invention is 6250-8000 meshes, so that the barium sulfate has good dispersity, and the whiteness and the brightness of the surface of the polypropylene drawer can be met. According to the invention, the spherical barium sulfate with low barium ion residue is compounded with the food-grade talcum powder to be used as a filler of the modified polypropylene material, the spherical barium sulfate has higher glossiness and whiteness, and is high in density, the shrinkage rate of a manufactured part is better than that of talcum powder, and the manufactured part is acid-base corrosion resistant, but the weight of the manufactured part is heavier, the glossiness of the talcum powder is not as good as that of the barium sulfate, and the weight of the manufactured part can be reduced by adding the talcum powder; the problem of warping deformation of the refrigerator freezing drawer can be solved, and the shrinkage rate at low temperature is improved; the freezing drawer which ensures that the modified polypropylene material can meet the requirements of food contact regulations of multiple countries provides safer products for users through comprehensive migration and heavy metal special migration tests, and reduces the risk of being penalized and recalled due to unqualified market inspection.
In the embodiment of the invention, the PP resin is an injection molding grade PP resin brand, including but not limited to the following commercial brands: zhongpetrochemical Z30S, zhongpetrochemical 548RQ and Mofu AP03B. The toughening agent in the raw materials adopts one or more of polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA) and ethylene propylene diene monomer grafted maleic anhydride copolymer (EPDM-g-MA).
In order to improve the adhesion and the dispersibility of the filler and the matrix resin and improve the mechanical property of the modified polypropylene material, the raw materials are added with a coupling agent, and the coupling agent is one or more of an aluminate coupling agent, a silane coupling agent and a titanate coupling agent. Through the surface treatment of the coupling agent, the lipophilicity of the barium sulfate surface is increased, so that the cohesiveness of the barium sulfate and matrix resin and the dispersibility of the barium sulfate in a matrix are enhanced, and the mechanical properties, particularly the impact toughness and the elongation at break of the polypropylene composite material are obviously improved.
In the embodiment of the invention, the cold-resistant plasticizer is added to assist in enhancing the toughness of the polypropylene material, so that the toughness of the polypropylene material under an ultralow temperature condition can be met, and particularly, the modified polypropylene material can still maintain high toughness at the temperature of below-40 ℃. When the cold-resistant plasticizer and the PP resin are heated and melted together, small molecules of the cold-resistant plasticizer can be inserted between polypropylene polymer molecular chains, so that the attraction among the polypropylene molecular chains is weakened, the distance among the molecular chains is increased, the possibility of movement of the polypropylene molecular chains is increased, the entanglement among the polypropylene molecular chains is reduced, the crystallinity of the polypropylene molecular chains is reduced, the polypropylene can be subjected to glass transition at a lower temperature, the plasticity of the polypropylene is increased, and the possibility of cracking of the modified polypropylene drawer at an ultralow temperature is finally reduced. The cold-resistant plasticizer in the invention adopts one or more of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultrahigh molecular weight polyethylene.
The lubricant used in the embodiment of the invention is oleamide, and the antioxidant used is a compound antioxidant, and comprises tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite, wherein the compound ratio of the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester to the tris (2, 4-di-tert-butylphenyl) phosphite is 1: 1.
The preparation method of the modified polypropylene material for the refrigerator freezing drawer comprises the following steps:
respectively weighing PP resin, barium sulfate, cold-resistant plasticizer, coupling agent, toughening agent, lubricant and antioxidant according to the set mass parts, putting the PP resin, the barium sulfate, the cold-resistant plasticizer, the coupling agent, the toughening agent, the lubricant and the antioxidant into a high-speed stirrer, and stirring for 10-30 minutes until all the components are uniformly mixed to obtain a mixture A;
weighing talcum powder according to the set mass portion, and uniformly stirring the talcum powder and the mixture A again for 10-15 minutes to obtain a final mixture B;
starting the double-screw extruder, and putting the mixture B into the double-screw extruder for extrusion granulation, wherein the temperature of the double-screw extruder is set as follows: the temperature of the pre-melting temperature zone is set to be any value between 140 ℃ and 160 ℃, the temperature of the first zone is set to be any value between 170 ℃ and 190 ℃, the temperature of the second zone is set to be any value between 190 ℃ and 220 ℃, the temperature of the third zone is set to be any value between 210 ℃ and 220 ℃, the temperature of the fourth zone is set to be any value between 200 ℃ and 220 ℃, and the temperature of the discharge hole temperature zone is set to be any value between 190 ℃ and 200 ℃; the rotating speed of the screw is set to be any value between 300r/min and 400 r/min; and carrying out melt blending, extrusion, cooling and granulation on the mixture B, fully melting and compounding the materials under the shearing, mixing and conveying of a screw, and carrying out extrusion granulation and drying to obtain the modified polypropylene material for the refrigerator freezing drawer.
In the steps of the preparation method, the adding sequence of the barium sulfate and the talcum powder is different, the barium sulfate is firstly added and evenly mixed with other materials to obtain a mixture, the talcum powder is then added and evenly mixed with the mixture again, and the compatibility of the obtained product is improved by improving the adding process.
The modified polypropylene material for the refrigerator freezing drawer obtained by the preparation method is applied to the refrigerator freezing drawer, the freezing drawer which can meet the requirements of national standards and European Union food contact regulations can meet the food grade requirements through comprehensive migration and heavy metal special migration tests, the possibility of cracking of the freezing drawer at ultralow temperature is reduced, and the high-gloss freezing drawer is obtained.
In order to more clearly and specifically describe the modified polypropylene material for the refrigerator freezer drawer, the preparation method thereof and the refrigerator freezer drawer provided by the embodiment of the invention, the following description will be given with reference to specific embodiments.
Example 1
Weighing the following raw materials in parts by weight: 65 parts of PP resin, 20 parts of barium sulfate, 10 parts of talcum powder, 2 parts of cold-resistant plasticizer, 0.3 part of coupling agent, 2 parts of toughening agent, 0.5 part of lubricant and 0.2 part of antioxidant, wherein the trademark of the PP resin is Zhongpetrochemical Z30S, the barium sulfate is spherical barium sulfate produced by a precipitation method, and the spherical barium sulfate is obtained by adding sulfuric acid again to remove free barium ions after the precipitation reaction is finished, the toughening agent is polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), the coupling agent is aluminate coupling agent, the cold-resistant plasticizer is diisodecyl adipate, the lubricant is oleamide, and the antioxidant is pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite in a ratio of 1: 1.
Putting the weighed PP resin, barium sulfate, diisodecyl adipate, an aluminate coupling agent, a polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), oleamide, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
uniformly stirring the weighed talcum powder and the mixture A again for 15 minutes to obtain a mixture B;
starting the twin-screw extruder, adding the mixture B into the twin-screw extruder, and setting the temperature of the twin-screw extruder as follows: the temperature of the pre-melting temperature zone is set to 145 ℃, the temperature of the first zone is set to 190 ℃, the temperature of the second zone is set to 210 ℃, the temperature of the third zone is set to 210 ℃, the temperature of the fourth zone is set to 210 ℃, and the temperature of the discharge hole temperature zone is set to 190 ℃; the rotating speed of the screw is set to be 300r/min; and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polypropylene material for the refrigerator freezing drawer.
Comparative example 1
Weighing the following raw materials in parts by mass: 65 parts of PP resin, 30 parts of calcium carbonate, 2 parts of cold-resistant plasticizer, 0.3 part of coupling agent, 2 parts of toughening agent, 0.5 part of lubricant and 0.2 part of antioxidant, wherein the grade of the PP resin is medium petrochemical Z30S, the toughening agent is polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), the coupling agent is aluminate coupling agent, the cold-resistant plasticizer is diisodecyl adipate, the lubricant is oleamide, and the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite which are compounded according to the ratio of 1: 1.
Putting the weighed PP resin, calcium carbonate, diisodecyl adipate, an aluminate coupling agent, a polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), oleamide, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture;
starting the twin-screw extruder, adding the mixture into the twin-screw extruder, and setting the temperature of the twin-screw extruder as follows: the temperature of the pre-melting temperature zone is set to 145 ℃, the temperature of the first zone is set to 190 ℃, the temperature of the second zone is set to 210 ℃, the temperature of the third zone is set to 210 ℃, the temperature of the fourth zone is set to 210 ℃, and the temperature of the discharge hole temperature zone is set to 190 ℃; the rotating speed of the screw is set to be 300r/min; and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polypropylene material for the refrigerator freezing drawer.
Comparative example 2
Weighing the following raw materials in parts by weight: 65 parts of PP resin, 20 parts of barium sulfate, 10 parts of talcum powder, 2 parts of cold-resistant plasticizer, 0.3 part of coupling agent, 2 parts of toughening agent, 0.5 part of lubricant and 0.2 part of antioxidant, wherein the grade of the PP resin is Zhongpetrochemical Z30S, the barium sulfate is common barium sulfate, the toughening agent is polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), the coupling agent is aluminate coupling agent, the cold-resistant plasticizer is diisodecyl adipate, the lubricant is oleamide, the antioxidant is pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite are compounded according to the ratio of 1: 1.
Putting the weighed PP resin, barium sulfate, diisodecyl adipate, an aluminate coupling agent, a polyolefin elastomer grafted maleic anhydride copolymer (POE-g-MA), oleamide, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris (2, 4-di-tert-butylphenyl) phosphite into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
uniformly stirring the weighed talcum powder and the mixture A again for 15 minutes to obtain a mixture B;
starting the twin-screw extruder, adding the mixture B into the twin-screw extruder, and setting the temperature of the twin-screw extruder as follows: the temperature of the pre-melting temperature zone is set to 145 ℃, the temperature of the first zone is set to 190 ℃, the temperature of the second zone is set to 210 ℃, the temperature of the third zone is set to 210 ℃, the temperature of the fourth zone is set to 210 ℃, and the temperature of the discharge hole temperature zone is set to 190 ℃; the rotating speed of the screw is set to 300r/min; and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polypropylene material for the refrigerator freezing drawer.
Performance test
The modified polypropylene materials obtained in example 1 and comparative example 1 were prepared into sheet samples, and subjected to a comprehensive migration test of 4% acetic acid of GB1806 standard and 3% acetic acid of regulation (EU) No.10/2011& (EU) No. 2020/1245.
Wherein the limit of the total migration amount is 10mg/dm < 2 > according to the national standard; the contents of the European Union Plastic food contact Material and article code (EU) No.10/2011& (EU) No.2020/1245 comprehensive migration test method are referred to in Table 1, and the specific steps are as follows: the ratio of the soaking area of the PP plastic to the soaking solution is 0.6dm2/100ml, according to the ratio, the sample is respectively soaked in three simulation solutions of 10% ethanol, 3% acetic acid and olive oil (or substitute 95% ethanol and isooctane), one round is performed every 10 days, 3 rounds are performed in total, and the total migration content in the soaking solution in each round is tested.
And repeating the migration test for three times, judging according to the test result of the third time, but simultaneously requiring that the numerical value of the migration test for three times is in a decreasing trend, namely the migration test result of the second time is lower than that of the first time, the migration test result of the third time is lower than that of the second time, and the migration result of the third time is required not to exceed 10mg/dm < 2 >.
TABLE 1 European Union Plastic food contact materials and articles regulations full migration test method
The modified polypropylene materials obtained in example 1 and comparative example 2 were prepared into sheet samples, and subjected to heavy metal specific migration test according to the regulation of (EU) No.10/2011& (EU) No. 2020/1245.
The contents of the test method for the special migration of heavy metal in European Union plastic food contact materials and article regulations (EU) No.10/2011& (EU) No.2020/1245 refer to the contents in Table 2, and the specific steps are as follows: the ratio of the soaking area of the PP plastic to the soaking solution is 0.6dm2/100ml, and according to the ratio, the sample is soaked in 3 percent acetic acid simulation solution for 3 times every 10 days, and the migration content of 23 heavy metals in each round of soaking solution is tested.
And repeating the migration test for three times, judging according to the test result of the third time, but simultaneously requiring that the value of the migration test for three times is in a descending trend, namely the result of the migration test for the second time is lower than that of the migration test for the first time, the result of the migration test for the third time is lower than that of the migration test for the second time, and the result of the migration test for the third time is not more than the limit value, wherein the content of barium metal is required to be less than 1mg/kg.
TABLE 2 European Union Plastic food contact materials and articles regulations heavy metal Special migration test method
The results of the test for the migration of all the surfaces of the sheet samples made of the modified polypropylene materials obtained in example 1 and comparative example 1 according to the above method are shown in Table 3, and the results of the test for the migration of heavy metals specific to heavy metals of the sheet samples made of the modified polypropylene materials obtained in example 1 and comparative example 2 according to the above method are shown in Table 4.
Table 3 test table for overall migration of modified polypropylene materials of example 1 and comparative example 1
Table 4 test table for special heavy metal migration of modified polypropylene materials in example 1 and comparative example 2
From the above, according to the modified polypropylene material obtained by the technical scheme of the invention, the comprehensive migration test of 3% acetic acid is carried out according to the (EU) No.10/2011& (EU) No.2020/1245 rule, the result is less than 5mg/dm2, the comprehensive migration test of 4% acetic acid is carried out according to the GB1806 standard, the result is less than 5mg/dm2, and according to the special migration test of heavy metal of the (EU) No.10/2011& (EU) No.2020/1245 heavy metal, the content of barium metal is less than 0.1mg/kg, the requirements of the comprehensive migration test and the special migration test of heavy metal required by the national standard and the EU food contact rule are met, and the manufactured freezing drawer meets the food safety; in contrast, in comparative example 1, ordinary calcium carbonate is used as a filler to fill PP resin, and the modified polypropylene material prepared by the method has a result of 23.3mg/dm2 according to a 3% acetic acid overall migration test of European Union food contact regulation, and a result of 24.6mg/dm2 according to a national standard GB1806 standard, which cannot meet the requirements of national standards and European Union food contact regulation on overall migration; comparative example 2 the modified polypropylene material prepared by filling PP resin with ordinary barium sulfate has a barium metal content of 1.63mg/kg according to the special heavy metal migration test required by the eu food contact regulation, and does not satisfy the requirement of the special heavy metal migration test required by the eu food contact regulation.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
The foregoing description, for purposes of explanation, has been presented in conjunction with specific embodiments. However, the illustrative discussions above are not intended to be exhaustive or to limit the embodiments to the precise forms disclosed above. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles and the practical application, to thereby enable others skilled in the art to best utilize the embodiments and various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. The modified polypropylene material for the refrigerator freezing drawer is characterized by comprising the following components in parts by mass: 65-70 parts of PP resin, 15-20 parts of barium sulfate, 15-20 parts of talcum powder, 1-5 parts of cold-resistant plasticizer, 0.1-1.5 parts of coupling agent, 1.5-2 parts of toughening agent, 0.5-2 parts of lubricant and 0.2-1.5 parts of antioxidant, wherein the content of barium ions in the barium sulfate is lower than 10mg/kg, and the particle size range of the barium sulfate is 6250 meshes-8000 meshes; the particle size range of the talcum powder is 1000 meshes-1500 meshes.
2. The modified polypropylene material for refrigerator freezer drawers as claimed in claim 1, wherein the barium sulfate is spherical barium sulfate produced by precipitation method, and sulfuric acid is added again to remove free barium ions after the precipitation reaction is completed.
3. The modified polypropylene material for refrigerator freezer drawers as claimed in claim 1, wherein the cold-resistant plasticizer is at least one of dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultrahigh molecular weight polyethylene.
4. The modified polypropylene material for refrigerator freezer drawers as claimed in claim 1, wherein the coupling agent is at least one of an aluminate coupling agent, a silane coupling agent and a titanate coupling agent.
5. The modified polypropylene material for refrigerator freezer drawers as claimed in claim 1, wherein the toughening agent is at least one of polyolefin elastomer grafted maleic anhydride copolymer and ethylene propylene diene monomer grafted maleic anhydride copolymer.
6. The modified polypropylene material for refrigerator freezer drawers as claimed in claim 1, wherein the lubricant is oleamide, and the antioxidant is compounded with pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite at a ratio of 1: 1.
7. The preparation method of the modified polypropylene material for the refrigerator freezer drawer, which is disclosed by any one of claims 1 to 6, is characterized by comprising the following steps: respectively weighing PP resin, barium sulfate, cold-resistant plasticizer, coupling agent, toughening agent, lubricant and antioxidant in a high-speed mixer according to the set mass parts, and stirring for 10-30 minutes until all components are uniformly mixed to obtain a mixture A;
weighing talcum powder according to the set mass part, and uniformly stirring the talcum powder and the mixture A for 10-15 minutes to obtain a final mixture B;
and starting the double-screw extruder, putting the mixture B into the double-screw extruder for extrusion granulation, carrying out melt blending, extrusion, cooling and granulation, fully melting and compounding the materials under the shearing, mixing and conveying of the screws, and carrying out extrusion granulation and drying to obtain the modified polypropylene material for the refrigerator freezing drawer.
8. The preparation method of the modified polypropylene material for refrigerator freezer drawers as claimed in claim 7, wherein the temperature of the twin-screw extruder is set as follows: the temperature of a pre-melting temperature zone is 140-160 ℃, the temperature of a first zone is 170-190 ℃, the temperature of a second zone is 190-220 ℃, the temperature of a third zone is 210-220 ℃, the temperature of a fourth zone is 200-220 ℃, and the temperature of a discharge hole temperature zone is 190-200 ℃; the rotating speed of the screw is 300r/min-400r/min.
9. A refrigerator freezing drawer, characterized in that the drawer is prepared from the modified polypropylene material for the refrigerator freezing drawer according to any one of claims 1 to 6.
10. A refrigerator comprising the freezer drawer of claim 9.
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