CN114957863B - Heat-conducting polypropylene modified material for ice making box of refrigerator, preparation method and ice making box of refrigerator and refrigerator comprising heat-conducting polypropylene modified material - Google Patents
Heat-conducting polypropylene modified material for ice making box of refrigerator, preparation method and ice making box of refrigerator and refrigerator comprising heat-conducting polypropylene modified material Download PDFInfo
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- CN114957863B CN114957863B CN202210711723.7A CN202210711723A CN114957863B CN 114957863 B CN114957863 B CN 114957863B CN 202210711723 A CN202210711723 A CN 202210711723A CN 114957863 B CN114957863 B CN 114957863B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 98
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 90
- -1 polypropylene Polymers 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 60
- 239000000945 filler Substances 0.000 claims abstract description 53
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 24
- 230000000844 anti-bacterial effect Effects 0.000 claims description 23
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 8
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- BLDLNIJTYUZPCF-UHFFFAOYSA-N (2-methylmorpholin-2-yl)-(4-methylsulfanylphenyl)methanone Chemical compound C1=CC(SC)=CC=C1C(=O)C1(C)OCCNC1 BLDLNIJTYUZPCF-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000008014 freezing Effects 0.000 abstract description 6
- 238000007710 freezing Methods 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000001746 injection moulding Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000004599 antimicrobial Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing 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
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator, a preparation method, the ice making box for the refrigerator and the refrigerator containing the material, belongs to the technical field of modification and processing of high polymer composite materials, and can solve the technical problems that the existing method for improving the heat conductivity of polypropylene plastic has poor compatibility between a heat-conducting filler and a PP resin matrix, so that the mechanical property of the obtained material is reduced, cracking is easy to occur and the like, and the use requirement of a freezing chamber of the refrigerator cannot be met. The heat-conducting polypropylene modified material for the ice making box of the refrigerator comprises the following components in parts by weight: 30-45 parts of PP resin, 8-18 parts of toughening agent, 40-50 parts of heat conducting filler, 0.2-0.5 part of antioxidant, 0.4-1.0 part of special coupling agent, 0.5-2.0 parts of lubricant and 1.0-3.0 parts of antibacterial agent. The refrigerator ice making box produced by injection molding of the heat conducting polypropylene modified material provided by the invention has higher heat conductivity coefficient, not only can the ice making speed of the refrigerator be improved, but also the mechanical property of the ice making box can meet the requirement of the use environment.
Description
Technical Field
The invention belongs to the technical field of modification and processing of polymer composite materials, and particularly relates to a heat-conducting polypropylene modified material for an ice making box of a refrigerator, a preparation method, the ice making box for the refrigerator containing the heat-conducting polypropylene modified material and the refrigerator.
Background
With the rapid development of economy, the number of refrigerators in foreign countries is greatly increased, and users have high demands on the ice making function of the refrigerators, and meanwhile, the antibacterial performance and the food contact safety performance of the refrigerators are also very concerned. However, the current ice making speed of the refrigerator with the ice making function is generally slow, and the user experience is poor. The ice making box has application scene of freezing chamber of refrigerator, and low heat conductivity coefficient of ice making box material is one main factor of limiting heat conduction and affecting ice making speed.
At present, most of ice making boxes used in refrigerators with ice making function are made of polypropylene (PP) materials, and compared with ice making boxes made of metal materials, the ice making boxes made of polypropylene materials have the advantages of good corrosion resistance, easiness in processing and forming, low density, low price and the like, but the heat conductivity of pure polypropylene plastics is low, about 0.1-0.2W/(m.times.K), and the ice making speed is influenced. The current method for improving the thermal conductivity of polypropylene plastic is mainly to add filler with high thermal conductivity for filling blending modification, but because higher filler filling quantity is needed to reach the expected thermal conductivity, the filler is mostly inorganic and has poor compatibility with a polypropylene matrix, so that the mechanical property of the heat-conducting polypropylene composite material is reduced. In addition, the toughness of the polypropylene plastic is greatly reduced at low temperature, and the mechanical properties of the polypropylene plastic are further reduced due to the addition of the heat conducting filler and the antibacterial agent, so that the quality problems such as cracking and the like are easy to occur.
Therefore, the existing heat-conducting polypropylene material has poor low-temperature toughness and can not meet the use requirement of the refrigerator freezing chamber at low temperature.
Disclosure of Invention
Aiming at the technical problems that the existing method for improving the thermal conductivity of the polypropylene plastic has poor compatibility of the heat-conducting filler and the PP resin matrix, so that the mechanical property of the obtained material is reduced, cracking is easy to occur and the like, and the use requirement of the refrigerator freezing chamber at low temperature cannot be met, the invention provides the heat-conducting polypropylene modified material for the refrigerator ice making box, which has good dispersibility of the heat-conducting filler and gives consideration to the heat-conducting property and the mechanical property, and the preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The heat-conducting polypropylene modified material for the ice making box of the refrigerator comprises the following components in parts by weight:
30-45 parts of PP resin, 8-18 parts of toughening agent, 40-50 parts of heat conducting filler, 0.2-0.5 part of antioxidant, 0.4-1.0 part of special coupling agent, 0.5-2.0 parts of lubricant and 1.0-3.0 parts of antibacterial agent;
Wherein the special coupling agent is a compound containing a plurality of siloxane groups (Si-O-R), and the structural formula is shown as formula (1):
In one embodiment, the special coupling agent is prepared by taking a compound shown in a formula (2) and a compound shown in a formula (3) as reaction raw materials and performing condensation reaction under the action of an initiator;
wherein, the structural formula of the compound shown in the formula (2) is as follows:
the structural formula of the compound shown in the formula (3) is as follows:
in one embodiment, the initiator is selected from benzoyl peroxide or 2-methyl-4' - (methylthio) -2-morpholinophenone, and the initiator is reacted under ultraviolet irradiation.
In an embodiment, the PP resin is a polypropylene copolymer, the toughening agent is an ethylene-octene copolymer, the heat conductive filler is a spherical magnesium oxide powder, the antioxidant is selected from any one or two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite, the lubricant is selected from any one or more of polyethylene wax, stearate and dioctyl phthalate, and the antibacterial agent is an inorganic silver-loaded antibacterial agent or silver-loaded zirconium phosphate.
In one embodiment, the spheroidal magnesium oxide powder is a powder having an average particle diameter D90 of 30 μm and 5 μm, and is prepared according to (2:4): 1 mass ratio of the mixture.
In one embodiment, the antimicrobial agent is an inorganic silver-loaded antimicrobial agent or silver-loaded zirconium phosphate having an average particle size D90 of 1.8 μm.
The invention also provides a preparation method of the heat-conducting polypropylene modified material for the ice making box of the refrigerator, which comprises the following steps:
Weighing part of special coupling agent and heat conducting filler according to the mass percentage, adding the mixture of the special coupling agent and the heat conducting filler into a stirrer, and stirring for 2-5min at the rotating speed of 900-1300r/min to obtain a mixture A;
The mixture A is added into a double-screw extruder through a side feeding port;
Mixing the antibacterial agent with another part of special coupling agent, performing surface treatment, mixing with part of PP resin, an antioxidant and a lubricant to ensure that the mass fraction of the antibacterial agent in the antibacterial master batch is 20-25%, adding the antibacterial agent into a stirrer, stirring for 2-4min at the rotating speed of 700-900r/min, extruding out by a double-screw extruder, and granulating to obtain the antibacterial master batch;
mixing the antibacterial master batch with a toughening agent, the rest PP resin, an antioxidant and a lubricant, adding the mixture into a stirrer, and stirring the mixture for 3 to 5 minutes at the rotating speed of 1000 to 1500r/min to obtain a mixture B;
Adding the mixture B into a double-screw extruder through a main feed inlet, and obtaining the heat-conducting polypropylene modified material for the ice making box of the refrigerator through mixing, extrusion and granulation;
wherein, in the preparation step of the mixture A, the addition amount of the special coupling agent is 0.8-2.5wt% of the addition amount of the heat conducting filler, and in the preparation step of the antibacterial master batch, the addition amount of the special coupling agent is 1-2wt% of the addition amount of the antibacterial agent.
In one embodiment, the twin screw extruder screw aspect ratio L/d=32: 1-38:1, the screw rotating speed is 200-300r/min, and the temperatures of all the sections are respectively as follows: 160-210 ℃ in the first area, 200-220 ℃ in the second area, 200-220 ℃ in the third area, 200-220 ℃ in the fourth area, 190-210 ℃ in the fifth area, 190-210 ℃ in the sixth area and 200-220 ℃ in the machine head.
The invention provides a refrigerator ice making box, which is prepared from the heat-conducting polypropylene modified material for the refrigerator ice making box in any embodiment.
The invention provides a refrigerator, which comprises the refrigerator ice making box in the embodiment.
Compared with the prior art, the invention has the advantages and positive effects that:
1. According to the heat-conducting polypropylene modified material for the ice making box of the refrigerator, the special coupling agent is applied to the polypropylene modified material, and the heat-conducting filler is subjected to surface treatment, so that the dispersibility of the heat-conducting filler in a polypropylene matrix can be improved, the heat-conducting property and mechanical property of the polypropylene heat-conducting composite material are greatly improved, the use requirement of the refrigerator freezing chamber at low temperature is met, and the technical problem that the obtained composite material is poor in performance due to poor compatibility of the heat-conducting filler and the PP resin matrix at present is solved;
2. The refrigerator ice making box produced by injection molding of the heat conducting polypropylene modified material for the refrigerator ice making box provided by the invention has higher heat conductivity coefficient, not only can improve the ice making speed of the refrigerator, but also can ensure that the mechanical property of the ice making box meets the requirement of the use environment, and the quality problems such as cracking and the like can not occur after long-term use.
Drawings
FIG. 1 is an infrared spectrum of a special coupling agent provided in an embodiment of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator, which comprises the following components in parts by weight:
30-45 parts of PP resin, 8-18 parts of toughening agent, 40-50 parts of heat conducting filler, 0.2-0.5 part of antioxidant, 0.4-1.0 part of special coupling agent, 0.5-2.0 parts of lubricant and 1.0-3.0 parts of antibacterial agent;
Wherein the special coupling agent is a compound containing a plurality of siloxane groups (Si-O-R), and the structural formula is shown as formula (1):
In the embodiment, the invention provides the heat-conducting polypropylene modified material for the ice making box of the refrigerator, and the special coupling agent is applied to the polypropylene modified material and used for carrying out surface treatment on the heat-conducting filler, so that the dispersibility of the heat-conducting filler in a polypropylene matrix can be improved, the heat-conducting property and mechanical property of the heat-conducting composite material of the polypropylene can be greatly improved, the use requirement of the ice making box of the refrigerator at low temperature can be met, and the technical problem that the obtained composite material is poor in performance due to poor compatibility of the heat-conducting filler and the PP resin matrix at present can be solved.
It should be further described that, as can be seen from the description of the background art, the low-temperature toughness of the existing heat-conducting polypropylene material is poor, and the core factors that cannot meet the use requirement of the refrigerator freezing chamber at low temperature are as follows: the filler with high heat conductivity has too high addition amount and the antibacterial agent is added, so that the dispersibility of the filler and the antibacterial agent in the organic resin is poor, and the mechanical property and the heat conducting property of the organic resin are affected, which is one of the technical difficulties to be overcome by the invention. Therefore, the technical problem to be actually solved by the invention is how to improve the dispersibility of the heat conducting filler and the antibacterial agent in the organic resin, so that the prepared material has higher heat conductivity coefficient, improves the ice making speed of the refrigerator, and can also give consideration to mechanical properties, thereby meeting the requirements of the use environment of the refrigerator, and the technical difficulty to be overcome at present.
In order to fundamentally solve the problem, the present invention first contemplates using a special coupling agent as shown in formula (1) in the heat conductive polypropylene material, and as can be seen from the structural formula shown in formula (1), the special coupling agent used in the present invention is a novel coupling agent containing a plurality of siloxane groups (Si-O-R). The siloxane groups can form bonding between an organic phase (PP resin matrix) and an inorganic phase (magnesium oxide serving as a heat conducting filler) of the composite material through hydrolysis reaction, so that the compatibility between the organic phase and the inorganic phase is greatly improved, and the defect that the composite material obtained is poor in comprehensive performance due to poor compatibility between the organic phase and the inorganic phase originally is overcome. Compared with the traditional coupling agent, the novel coupling agent has more siloxane groups, and has better compatibility with an organic phase due to the great improvement of the segment length of the organic phase part, and has greatly improved combination probability with an inorganic phase due to a highly branched structure, so that the coupling efficiency, the compatibility between the organic phase and the inorganic phase and the improvement effect of the comprehensive performance of the material are greatly improved.
Further, the special coupling agent adopted by the invention has the following advantages compared with the traditional silane coupling agent (such as silane coupling agent KH-570):
(1) The total molecular weight and the segment length of the organic phase part are greatly improved, which is helpful for improving the compatibility with the polymer matrix;
(2) The high-branching structure is adopted, the number of active end group siloxane groups (bonding can be formed between the interface of the heat-conducting filler and the PP resin through hydrolysis, and the performance of the material is enhanced) is greatly improved, the coupling probability of the coupling agent and the inorganic filler is improved, the coupling effect is improved, the heat-conducting filler is prevented from agglomerating, and the heat-conducting filler is dispersed in the PP matrix more uniformly.
In conclusion, the characteristics improve the defects of low molecular weight, poor compatibility with polymers, fewer active end groups and low coupling efficiency of the conventional common coupling agent, so that the coupling effect is improved, the compatibility of a PP matrix and the heat-conducting filler is improved, the heat-conducting filler is further uniformly dispersed in the PP matrix, and the heat-conducting filler has important significance in improving the comprehensive properties (mechanical property, heat-conducting property and fluidity) of the obtained heat-conducting filler composite material.
Besides, besides the key effect of the special coupling agent in improving the dispersibility of the heat conducting filler in the organic resin, other components also play a role in coordination promotion, for example, besides the effect of the special coupling agent, the selection of the type, the particle size and the dosage of the heat conducting filler in the formula system is also key in improving the dispersibility of the heat conducting filler among the organic resins, so that the composite material with good comprehensive performance is obtained.
In a specific embodiment, the special coupling agent is prepared by taking a compound shown in a formula (2) and a compound shown in a formula (3) as reaction raw materials and performing condensation reaction under the action of an initiator;
wherein, the structural formula of the compound shown in the formula (2) is as follows:
the structural formula of the compound shown in the formula (3) is as follows:
In the above embodiment, the compound represented by the formula (2) is Vinyltriethoxysilane (VTES), the CAS number of which is: 754-05-2; the compound represented by formula (3) is trimethylol propane methyl trimethacrylate (TMTPMA), CAS number: 3290-92-4.
Further, the initiator used may be Benzoyl Peroxide (BPO), CAS number: 94-36-0, or photoinitiator 907 (2-methyl-4' - (methylthio) -2-morpholinophenone), CAS number: 71868-10-5, said initiator being reacted under ultraviolet irradiation.
In a specific embodiment, the PP resin is a polypropylene copolymer, the toughening agent is an ethylene-octene copolymer, the heat conducting filler is a spherical magnesium oxide powder, the antioxidant is selected from any one or two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite, the lubricant is selected from any one or more of polyethylene wax, stearate and dioctyl phthalate, and the antibacterial agent is an inorganic silver-loaded antibacterial agent or silver-loaded zirconium phosphate.
In one embodiment, the spheroidal magnesium oxide powder is a powder having an average particle diameter D90 of 30 μm and 5 μm, and is prepared according to the following (2:4): 1 mass ratio of the mixture.
In the above embodiment, the heat conductive filler-spherical magnesia powder is selected from powder with average particle diameter D90 of 30 μm and 5 μm, and the mass ratio of the two particle diameters can be specifically selected from 2:1, 3:1 and 4:1 or any value within the above-mentioned limiting range is selected according to actual needs to fall within the protection scope of the present invention. Meanwhile, the reason that the spherical magnesia powder with the two particle sizes is selected as the heat conducting filler is as follows: the mode of compounding the large particle size and the small particle size is adopted, the heat conducting fillers with different particle sizes are selected for mixing and filling, the effective accumulation among the heat conducting fillers can be improved, small particles can enter the space which cannot be occupied by large particles, more heat conducting chains or heat conducting nets are formed, and the heat conductivity coefficient of the material is effectively improved. Experiments show that in the embodiment, the ideal effect can be achieved by adopting the magnesium oxide powder with the D90 of 30 mu m and 5 mu m to compound according to the mass ratio of (2-4): 1.
In a specific embodiment, the antimicrobial agent is an inorganic silver-loaded antimicrobial agent or silver-loaded zirconium phosphate having an average particle size D90 of 1.8 μm.
In the above embodiment, the reason why the present invention selects an inorganic silver-carrying antibacterial agent or silver-carrying zirconium phosphate having an average particle diameter D90 of 1.8 μm as the antibacterial agent is that: the nano silver-carrying antibacterial agent is extremely easy to oxidize, is easy to cause phenomena of yellowing and the like of the workpiece, influences the appearance of the workpiece, and has higher cost. The silver-loaded antibacterial agent with larger particles (average particle diameter of 3-10 um) has poor compatibility with the polymer matrix, is easy to generate agglomeration phenomenon in the polymer matrix, has smaller specific surface area, cannot play a good antibacterial effect and can deteriorate the mechanical property of the composite material. Experiments show that the inorganic silver-carrying antibacterial agent or silver-carrying zirconium phosphate with the average particle diameter D90 of 1.8 mu m is adopted as antibacterial agent, so that the multiple requirements of the obtained material on good antibacterial performance, good mechanical property and low cost can be met.
The embodiment of the invention also provides a preparation method of the heat-conducting polypropylene modified material for the ice making box of the refrigerator, which comprises the following steps:
S1, weighing part of special coupling agent and heat conducting filler according to the mass percentage, and adding the mixture obtained by mixing the two into a stirrer to stir for 2-5min at the rotating speed of 900-1300r/min to obtain a mixture A;
S2, adding the mixture A into a double-screw extruder through a side feed port;
S3, mixing the antibacterial agent with another part of special coupling agent, performing surface treatment, mixing with part of PP resin, an antioxidant and a lubricant to ensure that the mass fraction of the antibacterial agent in the antibacterial master batch is 20-25%, adding the antibacterial agent into a stirrer, stirring for 2-4min at the rotating speed of 700-900r/min, extruding out through a double-screw extruder, and granulating to obtain the antibacterial master batch;
s4, mixing the antibacterial master batch with the toughening agent, the rest PP resin, the antioxidant and the lubricant, and adding the mixture into a stirrer to stir for 3-5min at the rotating speed of 1000-1500r/min to obtain a mixture B;
s5, adding the mixture B into a double-screw extruder from a main feed inlet, and obtaining the heat-conducting polypropylene modified material for the ice making box of the refrigerator through mixing, extrusion and granulation;
wherein, in the preparation step of the mixture A, the addition amount of the special coupling agent is 0.8-2.5wt% of the addition amount of the heat conducting filler, and in the preparation step of the antibacterial master batch, the addition amount of the special coupling agent is 1-2wt% of the addition amount of the antibacterial agent.
In the preparation method described in the above embodiment, the addition sequence of each raw material is limited, the special coupling agent is used for carrying out surface treatment on the heat conducting filler, so that filler particles can be uniformly dispersed in a polymer matrix, the comprehensive properties including mechanical property, heat conducting property and fluidity of the obtained composite material are improved, then the special coupling agent is used for carrying out surface treatment on the antibacterial agent, and the treated antibacterial agent is mixed with the raw materials such as PP matrix resin, antioxidant and lubricant.
In a specific embodiment, the twin screw extruder screw aspect ratio L/d=32: 1-38:1, the screw rotating speed is 200-300r/min, and the temperatures of all the sections are respectively as follows: 160-210 ℃ in the first area, 200-220 ℃ in the second area, 200-220 ℃ in the third area, 200-220 ℃ in the fourth area, 190-210 ℃ in the fifth area, 190-210 ℃ in the sixth area and 200-220 ℃ in the machine head.
The embodiment of the invention also provides a refrigerator ice making box, which is prepared from the heat-conducting polypropylene modified material for the refrigerator ice making box.
The embodiment of the invention also provides a refrigerator which comprises the refrigerator ice making box.
In order to more clearly and in detail describe the heat-conducting polypropylene modified material for ice making boxes of refrigerators, the preparation method, the ice making boxes for refrigerators and the refrigerators comprising the material provided by the embodiment of the invention, the following description will be made with reference to specific embodiments.
Example 1
The embodiment provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator and a preparation method thereof, and the heat-conducting polypropylene modified material comprises the following specific steps:
the heat-conducting polypropylene modified material for the ice making box of the refrigerator comprises the following components in parts by weight:
40 parts of PP resin, 10 parts of toughening agent, 45 parts of heat conducting filler, 2 parts of antibacterial agent, 2 parts of lubricant, 0.5 part of special coupling agent and 0.5 part of antioxidant;
The preparation method comprises the following steps:
(1) Weighing raw materials according to the formula, mixing 45 parts of weighed heat conducting filler with 0.47 part of special coupling agent, and placing the mixture into a stirrer to stir for 4min at the rotating speed of 1200r/min to obtain a mixture A;
(2) Adding the mixture A obtained in the step (1) into a double-screw extruder through a side feeding port;
(3) Mixing 2 parts of silver-loaded antibacterial agent with 0.03 part of special coupling agent, performing surface treatment, mixing with 5.3 parts of PP resin, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168 and 0.5 part of lubricant, adding into a stirrer, stirring for 3min at the speed of 800r/min, and extruding and granulating by a double-screw extruder to obtain antibacterial master batch;
(4) Mixing the antibacterial master batch with the weighed other material components, adding the mixture into a stirrer, and stirring at a rotating speed of 1200r/min for 4min to obtain a mixture B;
(5) Adding the mixture B obtained in the step (4) into a double-screw extruder through a main feed inlet, and mixing, extruding and granulating to obtain the heat-conducting polypropylene modified material for the ice making box of the refrigerator, wherein the length-diameter ratio of a screw rod of the double-screw extruder is=36:1, and the temperature and the screw rod rotating speed of each zone are respectively as follows: the temperature of the first area is 170 ℃, the temperature of the second area is 205 ℃, the temperature of the third area is 205 ℃, the temperature of the fourth area is 205 ℃, the temperature of the fifth area is 200 ℃, the temperature of the sixth area is 200 ℃, and the temperature of the machine head is 205 ℃; the screw speed was 270r/min.
Example 2
The embodiment provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator and a preparation method thereof, and the heat-conducting polypropylene modified material comprises the following specific steps:
the heat-conducting polypropylene modified material for the ice making box of the refrigerator comprises the following components in parts by weight:
40 parts of PP resin, 10 parts of toughening agent, 45 parts of heat conducting filler, 2 parts of antibacterial agent, 2 parts of lubricant, 1.0 part of special coupling agent and 0.5 part of antioxidant.
The preparation process was identical to example 1, except that the raw material formulation provided in this example was used.
Comparative example 1
The comparative example provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator and a preparation method thereof, and the heat-conducting polypropylene modified material comprises the following concrete steps:
the raw material formulation and the preparation method of the comparative example are the same as those of example 1, except that the coupling agent used for treating the heat conductive filler is silane coupling agent KH-570, and the coupling agent used for preparing the antibacterial master batch is titanate coupling agent.
Comparative example 2
The comparative example provides a heat-conducting polypropylene modified material for an ice making box of a refrigerator and a preparation method thereof, and the heat-conducting polypropylene modified material comprises the following concrete steps:
The raw material formulation and the preparation method of the comparative example are the same as those of example 2, except that the coupling agent used for treating the heat conductive filler is silane coupling agent KH-570, and the coupling agent used for preparing the antibacterial master batch is titanate coupling agent.
Performance testing
According to the invention, various performance tests are carried out on the polypropylene modified materials prepared in each example 2 and comparative example, and the specific test method and test results are as follows:
TABLE 1 Performance test Standard and results for Polypropylene modified materials obtained in examples 1-2 and comparative examples 1-2
As can be seen from the data shown in the table, the special coupling agent in the formula provided by the invention is adopted to replace the traditional coupling agent (such as silane coupling agent KH-570) to be added into the formula of the polypropylene modified material, and the heat conduction filler is subjected to surface treatment, so that the low-temperature notch impact strength, the elongation at break, the melt flow rate and the heat conduction coefficient of the finally obtained heat conduction modified PP granules are improved to a certain extent.
Infrared spectroscopic analysis
Since the special coupling agent used in the present invention is a novel coupling agent, fig. 1 shows an infrared spectrum of the special coupling agent used in the present invention, wherein the peak at 1720cm -1 is a-c=o functional group stretching vibration peak, the peak at 1640cm -1 is a-c=c functional group stretching vibration peak, and thus it can be seen that the special coupling agent of the present invention is significantly weakened compared with one Vinyl Triethoxysilane (VTES) which is a reactant, and the-c=c peak at 1640cm -1 is significantly weakened, and more stretching vibration peaks at 1720cm -1 are obtained, as can be seen by comparing the structural differences of the two, the synthetic reaction provided in the present invention should occur.
Claims (10)
1. The heat-conducting polypropylene modified material for the ice making box of the refrigerator is characterized by comprising the following components in parts by weight:
30-45 parts of PP resin, 8-18 parts of toughening agent, 40-50 parts of heat conducting filler, 0.2-0.5 part of antioxidant, 0.4-1.0 part of special coupling agent, 0.5-2.0 parts of lubricant and 1.0-3.0 parts of antibacterial agent;
Wherein the special coupling agent is a compound containing a plurality of siloxane groups (Si-O-R), and the structural formula is shown as formula (1):
the heat-conducting polypropylene modified material for the ice making box of the refrigerator is prepared by the following preparation method:
Weighing part of special coupling agent and heat conducting filler according to the mass percentage, adding the mixture of the special coupling agent and the heat conducting filler into a stirrer, and stirring for 2-5min at the rotating speed of 900-1300r/min to obtain a mixture A;
The mixture A is added into a double-screw extruder through a side feeding port;
Mixing the antibacterial agent with another part of special coupling agent, performing surface treatment, mixing with part of PP resin, an antioxidant and a lubricant to ensure that the mass fraction of the antibacterial agent in the antibacterial master batch is 20-25%, adding the antibacterial agent into a stirrer, stirring for 2-4min at the rotating speed of 700-900r/min, extruding out by a double-screw extruder, and granulating to obtain the antibacterial master batch;
mixing the antibacterial master batch with a toughening agent, the rest PP resin, an antioxidant and a lubricant, adding the mixture into a stirrer, and stirring the mixture for 3 to 5 minutes at the rotating speed of 1000 to 1500r/min to obtain a mixture B;
Adding the mixture B into a double-screw extruder through a main feed inlet, and obtaining the heat-conducting polypropylene modified material for the ice making box of the refrigerator through mixing, extrusion and granulation;
wherein, in the preparation step of the mixture A, the addition amount of the special coupling agent is 0.8-2.5wt% of the addition amount of the heat conducting filler, and in the preparation step of the antibacterial master batch, the addition amount of the special coupling agent is 1-2wt% of the addition amount of the antibacterial agent.
2. The heat-conducting polypropylene modified material for ice making boxes of refrigerators according to claim 1, wherein the special coupling agent is prepared by copolymerization reaction of a compound represented by formula (2) and a compound represented by formula (3) as reaction raw materials under the action of an initiator;
wherein, the structural formula of the compound shown in the formula (2) is as follows:
the structural formula of the compound shown in the formula (3) is as follows:
3. The heat conductive polypropylene modified material for ice making boxes of refrigerators according to claim 2, wherein the initiator is selected from benzoyl peroxide or 2-methyl-4' - (methylthio) -2-morpholinophenone, and the initiator reacts under ultraviolet irradiation.
4. The heat-conducting polypropylene modified material for ice making boxes of refrigerators according to claim 1, wherein the PP resin is a copolymerized polypropylene, the toughening agent is an ethylene-octene copolymer, the heat-conducting filler is a spherical-like magnesia powder, the antioxidant is selected from any one or two of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite, the lubricant is selected from any one or more of polyethylene wax, stearate and dioctyl phthalate, and the antibacterial agent is an inorganic silver-carrying antibacterial agent or silver-carrying zirconium phosphate.
5. The heat conductive polypropylene modified material for ice making boxes of refrigerators according to claim 4, wherein the spheroidal magnesium oxide powder is a powder having an average particle diameter D90 of 30 μm and 5 μm, and is prepared according to (2:4): 1 mass ratio of the mixture.
6. The heat conductive polypropylene modified material for ice making boxes of refrigerators according to claim 4, wherein the antibacterial agent is an inorganic silver-carrying antibacterial agent or silver-carrying zirconium phosphate having an average particle diameter D90 of 1.8 μm.
7. The method for preparing a heat conductive polypropylene modified material for ice making boxes of refrigerators according to any one of claims 1 to 6, comprising the steps of:
Weighing part of special coupling agent and heat conducting filler according to the mass percentage, adding the mixture of the special coupling agent and the heat conducting filler into a stirrer, and stirring for 2-5min at the rotating speed of 900-1300r/min to obtain a mixture A;
The mixture A is added into a double-screw extruder through a side feeding port;
Mixing the antibacterial agent with another part of special coupling agent, performing surface treatment, mixing with part of PP resin, an antioxidant and a lubricant to ensure that the mass fraction of the antibacterial agent in the antibacterial master batch is 20-25%, adding the antibacterial agent into a stirrer, stirring for 2-4min at the rotating speed of 700-900r/min, extruding out by a double-screw extruder, and granulating to obtain the antibacterial master batch;
mixing the antibacterial master batch with a toughening agent, the rest PP resin, an antioxidant and a lubricant, adding the mixture into a stirrer, and stirring the mixture for 3 to 5 minutes at the rotating speed of 1000 to 1500r/min to obtain a mixture B;
Adding the mixture B into a double-screw extruder through a main feed inlet, and obtaining the heat-conducting polypropylene modified material for the ice making box of the refrigerator through mixing, extrusion and granulation;
wherein, in the preparation step of the mixture A, the addition amount of the special coupling agent is 0.8-2.5wt% of the addition amount of the heat conducting filler, and in the preparation step of the antibacterial master batch, the addition amount of the special coupling agent is 1-2wt% of the addition amount of the antibacterial agent.
8. The method for producing a heat conductive polypropylene modified material for ice making boxes of refrigerators according to claim 7, wherein the aspect ratio of the twin-screw extruder screw L/d=32: 1-38:1, the screw rotating speed is 200-300r/min, and the temperatures of all the sections are respectively as follows: 160-210 ℃ in the first area, 200-220 ℃ in the second area, 200-220 ℃ in the third area, 200-220 ℃ in the fourth area, 190-210 ℃ in the fifth area, 190-210 ℃ in the sixth area and 200-220 ℃ in the machine head.
9. An ice making box for a refrigerator, which is characterized in that the ice making box for the refrigerator is prepared by using the heat conducting polypropylene modified material for the ice making box for the refrigerator according to any one of claims 1 to 6.
10. A refrigerator comprising the ice-making housing of the refrigerator according to claim 9.
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| JPH07331176A (en) * | 1994-06-06 | 1995-12-19 | Pola Chem Ind Inc | Coating composition |
| CN1919915A (en) * | 2005-08-26 | 2007-02-28 | 海尔集团公司 | Modified polypropylene material for refrigerator and manufacture method thereof |
| CN114395090A (en) * | 2022-02-18 | 2022-04-26 | 海信（山东）冰箱有限公司 | SBS-g-PS material, preparation method thereof and application thereof in low-temperature toughening modification of PP |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331176A (en) * | 1994-06-06 | 1995-12-19 | Pola Chem Ind Inc | Coating composition |
| CN1919915A (en) * | 2005-08-26 | 2007-02-28 | 海尔集团公司 | Modified polypropylene material for refrigerator and manufacture method thereof |
| CN114395090A (en) * | 2022-02-18 | 2022-04-26 | 海信（山东）冰箱有限公司 | SBS-g-PS material, preparation method thereof and application thereof in low-temperature toughening modification of PP |
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