CN118108990A - Modified polyethylene material, preparation method thereof, water pipe and refrigerator - Google Patents
Modified polyethylene material, preparation method thereof, water pipe and refrigerator Download PDFInfo
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- CN118108990A CN118108990A CN202410033699.5A CN202410033699A CN118108990A CN 118108990 A CN118108990 A CN 118108990A CN 202410033699 A CN202410033699 A CN 202410033699A CN 118108990 A CN118108990 A CN 118108990A
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- lldpe
- antibacterial
- modified polyethylene
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 50
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 50
- -1 polyethylene Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 93
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 93
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 89
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 42
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 39
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 39
- 239000000314 lubricant Substances 0.000 claims abstract description 23
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims description 42
- 239000006104 solid solution Substances 0.000 claims description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 33
- 239000000920 calcium hydroxide Substances 0.000 claims description 33
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 33
- 238000001125 extrusion Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 238000005469 granulation Methods 0.000 claims description 16
- 230000003179 granulation Effects 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 241000237502 Ostreidae Species 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000020636 oyster Nutrition 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 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 3
- 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
- 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
- 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
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 29
- 239000003242 anti bacterial agent Substances 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000009395 breeding Methods 0.000 description 4
- 230000001488 breeding effect Effects 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006015 heat resistant resin Polymers 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004711 α-olefin 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- 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
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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 invention discloses a modified polyethylene material, a preparation method thereof, a water pipe and a refrigerator, and belongs to the technical field of high polymer materials. The technical scheme includes that LLDPE resin, HDPE resin, lubricant, cold-resistant plasticizer and antibacterial master batch are used as raw materials, and the modified polyethylene material is prepared through the preparation steps of the antibacterial master batch and the modified LLDPE. The invention is applied to the aspect of a refrigerator, solves the problems that the traditional LLDPE water pipe cannot be applied to an ice maker of the refrigerator due to poor heat resistance and low temperature resistance and has no antibacterial property, and has the functions of high temperature resistance, low temperature resistance and antibacterial property.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified polyethylene material, a preparation method thereof, a water pipe and a refrigerator.
Background
Polyethylene (PE) has the characteristics of low cost, good chemical stability, high toughness, strong corrosion resistance and the like, and is widely applied to various industries. PE comprises High Density Polyethylene (HDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE). Among them, linear Low Density Polyethylene (LLDPE) is applied to a water pipe for an ice maker of a refrigerator.
At present, the common LLDPE water pipe has poor heat resistance and low temperature resistance. Specifically, a water valve configured by the ice making system is arranged in a refrigerator compressor bin, and a PE water pipe led out of the water valve needs to bear the temperature of 110 ℃ at most; part of the water pipes also participate in the foaming of the box body, and the highest instantaneous temperature is up to 100 ℃ during the foaming; however, the highest heat-resistant temperature of the common LLDPE material is 90 ℃, and a water pipe made of pure LLDPE resin can be melted due to high temperature in the production and application process of refrigerator products; 2. the PE water pipe configured by the ice making system is positioned in the freezing chamber environment, the lowest temperature is about minus 30 ℃, and the highest low temperature resistance of the common PE material is about minus 20 ℃.
At present, LLDPE water pipes which are suitable for being used in ice machines of refrigerators and resistant to high and low temperatures are not found on the market. In addition, the high-end refrigerator product is provided with ice making and drinking functions, and the drinking water flows from the water tap to the ice maker, so that the water pipe is a part with larger contact area in the part through which water flows. Although the refrigerator product is provided with the water filter, the refrigerator product is made of an activated carbon microporous filter membrane, and the refrigerator product is mainly used for removing disinfection byproducts, pesticides and other micro pollutants in water, but has no scale removal function, after the water pipe is used for a long time, some scale impurities are accumulated in the pipeline, microorganisms are attached to the attached surface, and when the water flow is slow or stops flowing, the microorganisms attached to the inner wall can evolve into bacteria, bacteria are formed by propagation after a period of time, the safety quality of the water is affected, and the safety of water and ice cubes consumed by a user can be further affected.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to solve the technical problems that the existing LLDPE water pipe cannot be applied to an ice maker of a refrigerator due to poor heat resistance and low temperature resistance and has no antibacterial property, and provides a modified polyethylene material with high-low temperature resistance and antibacterial function, a preparation method thereof, a water pipe and a refrigerator.
In order to solve the technical problems, the invention adopts the following technical scheme:
The invention provides a preparation method of a modified polyethylene material, which takes LLDPE resin, HDPE resin, lubricant, cold-resistant plasticizer and antibacterial master batch as raw materials, and prepares the modified polyethylene material through the preparation steps of the antibacterial master batch and the modified LLDPE; the preparation steps of the antibacterial master batch comprise: mixing water and zinc nitrate and fully dissolving, wherein the weight ratio of the water to the zinc nitrate is 0.9-1:29, any ratio of; adding water again and stirring continuously, adding calcium hydroxide at the same time, and standing for calcium hydroxide precipitation to obtain a first slurry, wherein the weight ratio of water to calcium hydroxide is 8.5-9: 1; carrying out solid-liquid separation on the first slurry to obtain a filter cake, and washing the filter cake to obtain an aqueous filter cake; grinding the water-containing filter cake into second slurry, and spray-drying to obtain solid solution antibacterial powder; and carrying out melt blending, extrusion, cooling and granulation on the solid solution antibacterial powder and LLDPE resin to obtain the antibacterial master batch.
Preferably, the melt blending, extruding, cooling, and granulating the solid solution antibacterial powder with the LLDPE resin comprises: adding 10-20 parts of solid solution antibacterial powder and 80-90 parts of LLDPE resin into a double-screw extruder, setting a pre-melting temperature zone of 150-155 ℃, a first zone of 170-175 ℃, a second zone of 175-180 ℃, a third zone of 180-185 ℃, a fourth zone of 190-200 ℃, a discharge port temperature zone of 200-205 ℃ and a screw speed of 280-320r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial master batch.
Preferably, the preparation steps of the modified LLDPE comprise: mixing the LLDPE resin and the HDPE resin in a high-speed mixer at normal temperature, adding the antibacterial master batch, the lubricant and the cold-resistant plasticizer, mixing at 75-85 ℃ to obtain a blend, and carrying out melt blending, extrusion, cooling and granulation on the blend to obtain the modified polyethylene material.
Preferably, said melt blending, extruding, cooling, granulating said blend comprises: adding the blend into a double-screw extruder, setting a pre-melting temperature zone 155-165 ℃, a first zone 175-185 ℃, a second zone 180-190 ℃, a third zone 185-195 ℃, a fourth zone 195-210 ℃, a discharge port temperature zone 210-215 ℃ and a screw rotating speed of 300-350r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polyethylene material.
Preferably, the LLDPE resin is used in an amount of 65 to 70 parts by weight, the HDPE resin is used in an amount of 20 to 45 parts by weight, the lubricant is used in an amount of 0.5 to 0.8 part by weight, the cold-resistant plasticizer is used in an amount of 0.5 to 2 parts by weight, and the antibacterial master batch is used in an amount of 3 to 8 parts by weight.
Preferably, the LLDPE resin is selected from linear low density polyethylene; the HDPE resin is selected from high density polyethylene; the lubricant is selected from polyethylene wax lubricants; the cold-resistant plasticizer is one or more selected from dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultra-high molecular weight polyethylene; the calcium hydroxide used in the preparation step of the antibacterial master batch is obtained by taking oyster shells as raw materials.
The invention also provides the modified polyethylene material prepared by the preparation method of the modified polyethylene material in any one of the technical schemes.
The invention also provides a water pipe, which is obtained by the extrusion molding step of the modified polyethylene material in any technical scheme.
Preferably, the extrusion molding step includes: adding the modified polyethylene material into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the water pipe is obtained by carrying out melt blending, extrusion and cooling on the materials in a pre-melting temperature area 155-160 ℃, a material cylinder area 160-165 ℃, a material cylinder area two 165-175 ℃, a material cylinder area three 175-185 ℃, a material cylinder area four 180-188 ℃, a flange 185-190 ℃, a machine head 190-195 ℃, a die 210-215 ℃ and a screw rotating speed of 30-35 r/min.
The invention also provides a refrigerator, wherein the water pipe in the technical scheme is arranged in the ice maker of the refrigerator.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides a preparation method of a modified polyethylene material, LLDPE resin is used as a raw material, and HDPE with a certain proportion is added, so that the shearing sensitivity of LLDPE is well improved, the production quality and efficiency of a water pipe are improved, and the problem of bacteria breeding of the water pipe is solved by adding antibacterial master batches;
the invention provides a water pipe which has high and low temperature resistance and antibacterial functions and can be well applied to a refrigerator.
Drawings
Fig. 1 is a schematic diagram of a preparation process flow of an antibacterial master batch provided by an embodiment of the invention.
Detailed Description
The following detailed description of the technical solutions in the specific embodiments of the present invention will be given with reference to the accompanying drawings. It is apparent that the described embodiments are only some specific implementations, but not all implementations, of the general technical solution of the present invention. All other embodiments, which are obtained by those skilled in the art based on the general inventive concept, fall within the scope of the present invention.
The invention provides a preparation method of a modified polyethylene material, which takes LLDPE resin, HDPE resin, lubricant, cold-resistant plasticizer and antibacterial master batch as raw materials, and prepares the modified polyethylene material through the preparation steps of the antibacterial master batch and the modified LLDPE; the preparation steps of the antibacterial master batch comprise: mixing water and zinc nitrate and fully dissolving, wherein the weight ratio of the water to the zinc nitrate is 0.9-1:29, any ratio of; adding water again and stirring continuously, adding calcium hydroxide at the same time, and standing for calcium hydroxide precipitation to obtain a first slurry, wherein the weight ratio of water to calcium hydroxide is 8.5-9: 1; carrying out solid-liquid separation on the first slurry to obtain a filter cake, and washing the filter cake to obtain an aqueous filter cake; grinding the water-containing filter cake into second slurry, and spray-drying to obtain solid solution antibacterial powder; and carrying out melt blending, extrusion, cooling and granulation on the solid solution antibacterial powder and LLDPE resin to obtain the antibacterial master batch. The invention provides a preparation method of a modified polyethylene material, LLDPE resin is used as a raw material, and HDPE with a certain proportion is added, so that the shearing sensitivity of LLDPE is well improved, the production quality and efficiency of a water pipe are improved, and the problem of bacteria breeding of the water pipe is solved by adding antibacterial master batches.
Specifically, because the LLDPE molecular chain has amorphous phase, and the acting force among molecules in the phase is weak, the molecular chain is easy to generate relative movement when heated, so the LLDPE has low heat-resistant temperature, and particularly is easy to soften to melt at high temperature, thereby seriously affecting the use effect and service life of the LLDPE. Generally, heat-resistant modification can be performed by filling, reinforcing, high polymer alloy and chemical crosslinking, however, the modification method may influence the performance of LLDPE, and the heat-resistant temperature of HDPE is higher than that of LLDPE. At the same time, LLDPE has less shear sensitivity because it has a narrow molecular weight distribution and short chain branching, and during shear (e.g., extrusion) LLDPE maintains a greater viscosity, requiring higher melt temperatures and pressures. In extrusion molding, HDPE with a certain proportion is added, so that the shearing sensitivity of LLDPE can be well improved, and the quality and efficiency of water pipe production can be improved. In addition, aiming at the problem of bacteria breeding in water pipes, the antibacterial master batch needs to be added, and the antibacterial agent adopts the solid solution antibacterial LLDPE master batch which is prepared by taking natural oyster shells as raw materials and has main components of calcium hydroxide and zinc ions.
In general, heat resistant modifiers may be added to the plastic to increase the heat resistant temperature of the plastic, but may affect other properties inherent to the plastic itself. There is also a common method of mixing a high heat-resistant resin into a low heat-resistant resin to provide heat resistance thereof, and there is an advantage in that the heat resistance of the resin is improved while other properties inherent in the low heat-resistant resin are not substantially affected. The Vicat softening temperature is the heat resistance index temperature of the material, the Vicat softening temperature of LLDPE is about 90 ℃, and the Vicat softening temperature of HDPE is about 125 ℃, the invention adopts the blending of HDPE and LLDEP to improve the heat resistance temperature of LLDPE. Specifically, as can be seen from comparing these key performance indexes of LLDPE and HDPE with Table 1, the HDPE has a higher heat resistance temperature than LLDPE, so that the HDPE resin is blended with LLDPE according to a certain proportion, the heat resistance of LLDPE can be improved, but the melt indexes of LLDPE and HDPE are basically equivalent, so that the compatibility is ensured.
Table 1 comparison of LLDPE and HDPE Performance index
| Performance index | Tensile Strength | Impact Strength | Environmental stress crack resistance | Heat resistance | Gloss level |
| LLDPE | Low and low | Equivalent to | Equivalent to | Low (softening point 94-108 ℃ C.) | High height |
| HDPE | High height | Equivalent to | Equivalent to | High (softening point 125-135 ℃ C.) | Low and low |
In addition, the toughness of LLDPE materials can be enhanced by the cold-resistant plasticizer in an auxiliary way, so that the toughness under the ultralow temperature condition can be met. When the cold-resistant plasticizer and LLDPE resin are heated and melted together, small molecules of the cold-resistant plasticizer are inserted between LLDPE polymer molecular chains, so that attractive force between LLDPE molecular chains is weakened, the distance between the molecular chains is increased, the movement possibility of LLDPE molecular chains is increased, entanglement between the LLDPE molecular chains is reduced, crystallinity of the LLDPE molecular chains is reduced, and glass transition of LLDPE can be carried out at a lower temperature, and therefore, the plasticity of the LLDPE is increased, and finally, the toughness of an LLDPE water pipe at an ultralow temperature is improved.
With respect to the realization of antibacterial functions, inorganic antibacterial agents are the most effective and safer class of antibacterial agents recognized by the industry, and in particular silver ion antibacterial agents are most widely used. However, an antibacterial agent is difficult to simultaneously have long-acting and quick-acting effects, the mechanism of the silver-containing antibacterial agent is that silver ions are gradually dissolved outwards by means of moisture to inhibit bacteria attached to the surface of a product, and an antibacterial function is realized. Meanwhile, the silver ion antibacterial agent has the defects of high price, easy yellowing of products, no high temperature resistance and the like. In order to solve the disadvantages of silver ion antibacterial agents, we consider that natural oyster shells are taken as the basis, calcium carbonate is obtained by washing and coarse crushing, then inorganic antibacterial agents containing zinc ions are prepared by adopting a solid solution method, and the manufacturing process of antibacterial master batches is shown in figure 1. Wherein, the principle of solid solution: solid solution inorganic antibacterial agent Solid solution (Solid solution) is a chemical phenomenon widely existing in nature. Solid solutions refer to a substance in which crystals (solutes) of one substance are dissolved in the form of ions, atoms or molecules in a lattice of another crystal (solvent). Or two ions or ion groups are exchanged and mutually dispersed and fused to form the mixed crystal phenomenon of the material. A great deal of spectral detection on materials after solid solution reaction by using an X-ray spectral reflectometer proves that: the new material can not observe the spectrum of independent and inherent strength of two elements, and only the spectrum of mixed crystallization of two elements, namely the crystal lattice type of the solvent is not changed, and certain strength and original performance can still be maintained; although the concentration of the raw materials, the amount of dissolved raw materials and the method can be different, different new performances are added after the two different elements are mixed in solid solution. The natural oyster shell belongs to a biomass material, is very easy to obtain, can reduce the influence of the environment by collecting the oyster shell of waste gas, and obtains the low-price calcium hydroxide through processing. Calcium hydroxide is commonly called slaked lime, is a white powdery solid, can generate hydroxyl ions with water, and can reduce the activity of toxic organisms and kill various fungi. The material is nontoxic or approximately nontoxic, has excellent high temperature resistant property and white color, and can be used as a heat stabilizer and a light stabilizer. However, calcium hydroxide alone has the disadvantage that it gradually becomes calcium carbonate with carbonic acid gas after contacting with the atmosphere, and crystals are easily formed in water. However, if divalent metals such as Mg, ca, zn, etc. are solid-dissolved in calcium hydroxide to form a completely new solid solution, the above-mentioned drawbacks can be overcome and the acid resistance can be improved. Zinc ion is one of antibacterial metal ions carried by inorganic antibacterial agents, and is a common antibacterial material which is safe, low in cost and free from color change. However, the zinc ion has a low antibacterial activity compared with silver ion. However, if Zn divalent metal is dissolved in calcium hydroxide to form a brand new solid solution, high concentration Zn ions can be slowly released in water, so as to achieve the antibacterial effect.
According to the technical scheme, the application of a solid solution technology in the preparation of the antibacterial master batch is realized by limiting the preparation method of the antibacterial master batch, specifically, the natural oyster shell is processed to obtain the calcium hydroxide, the calcium hydroxide and the zinc nitrate generate a solid solution reaction, divalent Zn ions are dissolved in the calcium hydroxide, after the calcium hydroxide and the zinc ions pass through the solid solution technology, the solid solution antibacterial agent is neither divalent migration zinc metal ions nor hydroxide, the defect of breeding of two materials is effectively overcome, and compared with the original calcium hydroxide, the calcium hydroxide can not react to become calcium carbonate after being contacted with the atmosphere and water, and the antibacterial master batch can be effectively antibacterial. Calcium hydroxide is a slightly soluble or insoluble substance in water, so that zinc ions in calcium hydroxide lattices are slightly soluble, and the solid solution antibacterial agent has quick-acting antibacterial effect and long-acting antibacterial effect due to higher speed and larger release amount. In addition, the antibacterial master batch contains a certain amount of calcium hydroxide, the calcium hydroxide can be used as a heat stabilizer, and the antibacterial master batch has the characteristics of white color, light stability, ultraviolet light absorption capability, no color change caused by light and heat, and further whiteness of a product, and the HDPE can influence the glossiness of LLDPE, so that the modified LLDPE resin does not need to be additionally added with an antioxidant, a heat stabilizer and other inorganic fillers to increase the whiteness of the product.
In a preferred embodiment, the melt blending, extruding, cooling, and pelletizing the solid solution antimicrobial powder with the LLDPE resin comprises: adding 10-20 parts of solid solution antibacterial powder and 80-90 parts of LLDPE resin into a double-screw extruder, setting a pre-melting temperature zone of 150-155 ℃, a first zone of 170-175 ℃, a second zone of 175-180 ℃, a third zone of 180-185 ℃, a fourth zone of 190-200 ℃, a discharge port temperature zone of 200-205 ℃ and a screw speed of 280-320r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial master batch. The technical scheme specifically limits the melt extrusion process of the antibacterial master batch, and the reason is that the melt extrusion process can better ensure the antibacterial performance of the antibacterial master batch and the compatibility of the antibacterial master batch with other raw materials, and ensure that the performance of the obtained modified LLDPE resin meets the requirements. Wherein the grain diameter D50 of the solid solution zinc ion antibacterial agent grain in the solid solution antibacterial powder is less than 1.27 mu m.
In a preferred embodiment, the preparation steps of the modified LLDPE comprise: mixing the LLDPE resin and the HDPE resin in a high-speed mixer at normal temperature, adding the antibacterial master batch, the lubricant and the cold-resistant plasticizer, mixing at 75-85 ℃ to obtain a blend, and carrying out melt blending, extrusion, cooling and granulation on the blend to obtain the modified polyethylene material. Further, said melt blending, extruding, cooling, granulating said blend comprises: adding the blend into a double-screw extruder, setting a pre-melting temperature zone 155-165 ℃, a first zone 175-185 ℃, a second zone 180-190 ℃, a third zone 185-195 ℃, a fourth zone 195-210 ℃, a discharge port temperature zone 210-215 ℃ and a screw rotating speed of 300-350r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polyethylene material.
In a preferred embodiment, the LLDPE resin is used in an amount of any one of 65 to 70 parts by weight, the HDPE resin is used in an amount of any one of 20 to 45 parts by weight, the lubricant is used in an amount of any one of 0.5 to 0.8 parts by weight, the cold-resistant plasticizer is used in an amount of any one of 0.5 to 2 parts by weight, and the antibacterial master batch is used in an amount of any one of 3 to 8 parts by weight. It will be appreciated that the LLDPE resin may also be used in an amount of 66 parts, 67 parts, 68 parts, 69 parts and any point value within its range; the HDPE resin may also be used in an amount of 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, and any point value within its range; the amount of lubricant may also be 0.6 parts, 0.7 parts, and any point value within its range; the dosage of the cold-resistant plasticizer can be 1.0 part, 1.5 parts and any point value in the range thereof; the amount of the antibacterial master batch may be 4 parts, 5 parts, 6 parts, 7 parts, and any point value within the range thereof.
In a preferred embodiment, the LLDPE resin is selected from the group consisting of linear low density polyethylene; the HDPE resin is selected from high density polyethylene; the lubricant is selected from polyethylene wax lubricants; the cold-resistant plasticizer is one or more selected from dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultra-high molecular weight polyethylene; the calcium hydroxide used in the preparation step of the antibacterial master batch is obtained by taking oyster shells as raw materials. Wherein the linear low density polyethylene is structurally different from the general low density polyethylene in that long chain branches are not present, is a copolymer of ethylene and a small amount of higher alpha-olefins (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) polymerized under high or low pressure in the presence of a catalyst, and has a density of between 0.915 and 0.940 g/cc, which is a type of extrusion grade LLDPE resin, including but not limited to the following commercial grades: medium petrochemical DFDA-7042, korean SK RG300U, eksen LL1002KW. The LDPE is high-density polyethylene and is usually manufactured by a Ziegler-Natta polymerization method, and is characterized in that the molecular chains have no branched chains, so that the molecular chains are orderly distributed, and the density is higher. The process initiates polymerization reaction with ethylene as raw material and oxygen or organic peroxide as initiator in a tubular or kettle type low pressure reactor, and the grades of the grade HDPE resins include, but are not limited to, the following commercial brands: U.S. Dow 2103-90AE, medium Petroleum TUB121N3000, LG chemical HDPE PD0390. This example defines that the lubricant is a polyethylene wax lubricant that reduces mechanical friction and in-mixture friction in the PE material reprocessing species.
The invention also provides the modified polyethylene material prepared by the preparation method of the modified polyethylene material in any one of the technical schemes. The modified polyethylene material has the characteristics of heat resistance, low temperature resistance and good antibacterial property.
The invention also provides a water pipe, which is obtained by the extrusion molding step of the modified polyethylene material in any technical scheme. In a preferred embodiment, the extrusion molding step includes: adding the modified polyethylene material into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the water pipe is obtained by carrying out melt blending, extrusion and cooling on the materials in a pre-melting temperature area 155-160 ℃, a material cylinder area 160-165 ℃, a material cylinder area two 165-175 ℃, a material cylinder area three 175-185 ℃, a material cylinder area four 180-188 ℃, a flange 185-190 ℃, a machine head 190-195 ℃, a die 210-215 ℃ and a screw rotating speed of 30-35 r/min. The water pipe has the functions of high and low temperature resistance and antibacterial, and can be well applied to a refrigerator.
The invention also provides a refrigerator, wherein the water pipe in the technical scheme is arranged in the ice maker of the refrigerator.
In order to more clearly and in detail describe the modified polyethylene material, the preparation method thereof, the water pipe and the refrigerator provided by the embodiment of the invention, the following description will be made with reference to specific embodiments.
Example 1
The following is a heat and low temperature resistant antibacterial LLDPE material of this example:
Weighing the following raw materials in parts by weight:
70 parts of LLDPE resin, 30 parts of HDPE resin, 0.5 part of lubricant, 1 part of cold-resistant plasticizer and 5 parts of antibacterial master batch.
1. Preparation of antibacterial master batches:
1. adding 0.5kg of water and 14.5kg of zinc nitrate into the reaction kettle simultaneously, and stirring for full dissolution;
2. Then 633.6kg of water is added, stirring is continuously carried out, 70.4kg of calcium hydroxide is added, and calcium hydroxide precipitation is prevented, and stirring is continued for 20-30 minutes;
3. Injecting the slurry in the reaction kettle into a centrifuge, centrifuging for 10 minutes at 6000 rpm to realize solid-liquid separation, and preparing a filter cake;
4. washing with clear water in a centrifuge for more than two times, and finally preparing an aqueous filter cake;
5. Grinding the filter cake into slurry by a wet grinder, and spray-drying to obtain powder, thereby obtaining the particle size of the solid solution zinc ion antibacterial agent with D50 less than 1.27 mu m.
6. The solid solution antibacterial powder and LLDPE resin are respectively added into a double-screw extruder according to the mass fractions of 10-20 parts and 80-90 parts, and the temperature of a pre-melting temperature zone 153 ℃, a first zone 172 ℃, a second zone 175 ℃, a third zone 180 ℃, a fourth zone 195 ℃ and a discharge port temperature zone 200 ℃; the rotating speed of the screw is 300r/min; and (3) carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial master batch.
2. Preparation of modified LLDPE: weighing 70 parts of LLDPE and 30 parts of HDPE according to the weight ratio, mixing for 60-90min at normal temperature in a high-speed mixer, adding 5 parts of antibacterial master batch, 0.5 part of lubricant and 1 part of cold-resistant plasticizer, mixing for 120min at 80 ℃, adding into a double-screw extruder, and pre-melting at 160 ℃, 175 ℃ in the first zone, 180 ℃ in the second zone, 185 ℃ in the third zone, 200 ℃ in the fourth zone and 210 ℃ in the temperature zone of a discharge hole; the rotating speed of the screw is 320r/min; and (3) carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial LLDPE material with heat resistance and low temperature resistance.
3. The heat and low temperature resistant antibacterial LLDPE material is added to a twin screw extruder, the temperature of the twin screw extruder is set as follows: 160 ℃ of a pre-melting temperature zone, 165 ℃ of a first charging barrel zone, 175 ℃ of a second charging barrel zone, 180 ℃ of a third charging barrel zone, 185 ℃ of a fourth charging barrel zone, 188 ℃ of a flange, 190 ℃ of a machine head and 215 ℃ of a die; the rotating speed of the screw is 34r/min; and carrying out melt blending, extrusion and cooling to obtain the heat-resistant low-temperature-resistant antibacterial LLDPE water pipe.
Example 2
The following is a heat and low temperature resistant antibacterial LLDPE material of this example:
Weighing the following raw materials in parts by weight:
70 parts of LLDPE resin, 30 parts of HDPE resin, 0.5 part of lubricant, 1 part of cold-resistant plasticizer and 5 parts of antibacterial master batch.
1. Preparation of antibacterial master batches:
1. adding 0.5kg of water and 14.5kg of zinc nitrate into the reaction kettle simultaneously, and stirring for full dissolution;
2. Then 633.6kg of water is added, stirring is continuously carried out, 70.4kg of calcium hydroxide is added, and calcium hydroxide precipitation is prevented, and stirring is continued for 20-30 minutes;
3. Injecting the slurry in the reaction kettle into a centrifuge, centrifuging for 10 minutes at 6000 rpm to realize solid-liquid separation, and preparing a filter cake;
4. washing with clear water in a centrifuge for more than two times, and finally preparing an aqueous filter cake;
5. Grinding the filter cake into slurry by a wet grinder, and spray-drying to obtain powder, thereby obtaining the particle size of the solid solution zinc ion antibacterial agent with D50 less than 1.27 mu m.
6. The solid solution antibacterial powder and LLDPE resin are respectively added into a double-screw extruder according to the mass fractions of 10-20 parts and 80-90 parts, and the temperature of a pre-melting temperature zone 153 ℃, a first zone 172 ℃, a second zone 175 ℃, a third zone 180 ℃, a fourth zone 195 ℃ and a discharge port temperature zone 200 ℃; the rotating speed of the screw is 300r/min; and (3) carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial master batch.
2. Preparation of modified LLDPE: weighing 85 parts of LLDPE and 15 parts of HDPE according to the weight ratio, mixing for 60-90min at normal temperature in a high-speed mixer, adding 5 parts of antibacterial master batch, 0.5 part of lubricant and 1 part of cold-resistant plasticizer, mixing for 120min at 80 ℃, adding into a double-screw extruder, and pre-melting at 160 ℃, 175 ℃ in the first zone, 180 ℃ in the second zone, 185 ℃ in the third zone, 200 ℃ in the fourth zone and 210 ℃ in the temperature zone of a discharge hole; the rotating speed of the screw is 320r/min; and (3) carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial LLDPE material with heat resistance and low temperature resistance.
3. The heat and low temperature resistant antibacterial LLDPE material is added to a twin screw extruder, the temperature of the twin screw extruder is set as follows: 160 ℃ of a pre-melting temperature zone, 165 ℃ of a first charging barrel zone, 175 ℃ of a second charging barrel zone, 180 ℃ of a third charging barrel zone, 185 ℃ of a fourth charging barrel zone, 188 ℃ of a flange, 190 ℃ of a machine head and 215 ℃ of a die; the rotating speed of the screw is 34r/min; and carrying out melt blending, extrusion and cooling to obtain the heat-resistant low-temperature-resistant antibacterial LLDPE water pipe.
Comparative example 1
Is a common LLDPE resin.
Performance testing
The materials prepared in examples 1,2 and comparative example 1 were fabricated into sheet samples, and the antibacterial test and vicat softening temperature test of ISO22196 were performed, and the test results are shown in table 2.
TABLE 2 Material Performance test results
Claims (10)
1. A preparation method of a modified polyethylene material is characterized in that LLDPE resin, HDPE resin, a lubricant, a cold-resistant plasticizer and antibacterial master batches are used as raw materials, and the modified polyethylene material is prepared through a preparation step of the antibacterial master batches and a preparation step of modified LLDPE; the preparation steps of the antibacterial master batch comprise:
Mixing water and zinc nitrate and fully dissolving, wherein the weight ratio of the water to the zinc nitrate is 0.9-1:29, any ratio of;
Adding water again and stirring continuously, adding calcium hydroxide at the same time, and standing for calcium hydroxide precipitation to obtain a first slurry, wherein the weight ratio of water to calcium hydroxide is 8.5-9: 1;
carrying out solid-liquid separation on the first slurry to obtain a filter cake, and washing the filter cake to obtain an aqueous filter cake;
Grinding the water-containing filter cake into second slurry, and spray-drying to obtain solid solution antibacterial powder;
And carrying out melt blending, extrusion, cooling and granulation on the solid solution antibacterial powder and LLDPE resin to obtain the antibacterial master batch.
2. The method of producing a modified polyethylene material according to claim 1, wherein said melt blending, extruding, cooling, granulating the solid solution antibacterial powder with the LLDPE resin comprises: adding 10-20 parts of solid solution antibacterial powder and 80-90 parts of LLDPE resin into a double-screw extruder, setting a pre-melting temperature zone of 150-155 ℃, a first zone of 170-175 ℃, a second zone of 175-180 ℃, a third zone of 180-185 ℃, a fourth zone of 190-200 ℃, a discharge port temperature zone of 200-205 ℃ and a screw speed of 280-320r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the antibacterial master batch.
3. The method of producing a modified polyethylene material according to claim 1, wherein said modified LLDPE production step comprises: mixing the LLDPE resin and the HDPE resin in a high-speed mixer at normal temperature, adding the antibacterial master batch, the lubricant and the cold-resistant plasticizer, mixing at 75-85 ℃ to obtain a blend, and carrying out melt blending, extrusion, cooling and granulation on the blend to obtain the modified polyethylene material.
4. A method of producing a modified polyethylene material according to claim 3, wherein said melt blending, extruding, cooling, granulating said blend comprises: adding the blend into a double-screw extruder, setting a pre-melting temperature zone 155-165 ℃, a first zone 175-185 ℃, a second zone 180-190 ℃, a third zone 185-195 ℃, a fourth zone 195-210 ℃, a discharge port temperature zone 210-215 ℃ and a screw rotating speed of 300-350r/min, and carrying out melt blending, extrusion, cooling and granulation to obtain the modified polyethylene material.
5. The method for producing a modified polyethylene material according to claim 1, wherein the amount of said LLDPE resin is selected from any one of 65 to 70 parts by weight, the amount of said HDPE resin is selected from any one of 20 to 45 parts by weight, the amount of said lubricant is selected from any one of 0.5 to 0.8 part by weight, the amount of said cold-resistant plasticizer is selected from any one of 0.5 to 2 parts by weight, and the amount of said antibacterial master batch is selected from any one of 3 to 8 parts by weight.
6. The method of making a modified polyethylene material according to claim 1, wherein said LLDPE resin is selected from the group consisting of linear low density polyethylene; the HDPE resin is selected from high density polyethylene; the lubricant is selected from polyethylene wax lubricants; the cold-resistant plasticizer is one or more selected from dioctyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, diisodecyl phthalate or ultra-high molecular weight polyethylene; the calcium hydroxide used in the preparation step of the antibacterial master batch is obtained by taking oyster shells as raw materials.
7. The modified polyethylene material produced by the production method of the modified polyethylene material according to any one of claims 1 to 6.
8. A water pipe, characterized in that it is obtained from the modified polyethylene material according to claim 7 by an extrusion molding step.
9. The water pipe of claim 8 wherein the extrusion step comprises: adding the modified polyethylene material into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the water pipe is obtained by carrying out melt blending, extrusion and cooling on the materials in a pre-melting temperature area 155-160 ℃, a material cylinder area 160-165 ℃, a material cylinder area two 165-175 ℃, a material cylinder area three 175-185 ℃, a material cylinder area four 180-188 ℃, a flange 185-190 ℃, a machine head 190-195 ℃, a die 210-215 ℃ and a screw rotating speed of 30-35 r/min.
10. A refrigerator characterized in that the water pipe of claim 8 or 9 is provided in an ice maker of the refrigerator.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000159898A (en) * | 1998-11-30 | 2000-06-13 | Matsushita Electric Ind Co Ltd | Antibacterial agent masterbatch |
| CN103524850A (en) * | 2013-10-10 | 2014-01-22 | 青岛颐世保塑料有限公司 | Special polyethylene antibiosis master batch |
| CN104206420A (en) * | 2014-08-07 | 2014-12-17 | 蔡惠萍 | Preparation method and application of silver-free powdery solid solution anti-bacterial agent |
| CN104277312A (en) * | 2013-07-04 | 2015-01-14 | 东港市远东节水灌溉设备有限公司 | Modified polyethylene pipe and making method thereof |
| WO2017088350A1 (en) * | 2015-11-26 | 2017-06-01 | 广东达华节水科技股份有限公司 | Anti-bacterial and ultraviolet irradiation-resistant pp/pe pipe material and preparation method therefor |
-
2024
- 2024-01-09 CN CN202410033699.5A patent/CN118108990A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000159898A (en) * | 1998-11-30 | 2000-06-13 | Matsushita Electric Ind Co Ltd | Antibacterial agent masterbatch |
| CN104277312A (en) * | 2013-07-04 | 2015-01-14 | 东港市远东节水灌溉设备有限公司 | Modified polyethylene pipe and making method thereof |
| CN103524850A (en) * | 2013-10-10 | 2014-01-22 | 青岛颐世保塑料有限公司 | Special polyethylene antibiosis master batch |
| CN104206420A (en) * | 2014-08-07 | 2014-12-17 | 蔡惠萍 | Preparation method and application of silver-free powdery solid solution anti-bacterial agent |
| WO2017088350A1 (en) * | 2015-11-26 | 2017-06-01 | 广东达华节水科技股份有限公司 | Anti-bacterial and ultraviolet irradiation-resistant pp/pe pipe material and preparation method therefor |
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