CN109485994B - Antibacterial and mildewproof polypropylene for outer barrel of drum washing machine and preparation method thereof - Google Patents
Antibacterial and mildewproof polypropylene for outer barrel of drum washing machine and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 184
- -1 polypropylene Polymers 0.000 title claims abstract description 176
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 171
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 171
- 238000005406 washing Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 77
- 239000002131 composite material Substances 0.000 claims abstract description 62
- 239000003365 glass fiber Substances 0.000 claims abstract description 43
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000000314 lubricant Substances 0.000 claims abstract description 37
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 36
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 239000007822 coupling agent Substances 0.000 claims abstract description 34
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 30
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 21
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229940043810 zinc pyrithione Drugs 0.000 claims abstract description 11
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 230000003449 preventive effect Effects 0.000 claims description 22
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000003429 antifungal agent Substances 0.000 claims description 4
- 229940121375 antifungal agent Drugs 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 230000032683 aging Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 description 24
- 241000894006 Bacteria Species 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
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- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000036541 health Effects 0.000 description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
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- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
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- 230000002035 prolonged effect Effects 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LUYIHWDYPAZCNN-UHFFFAOYSA-N 2-butyl-1,2-benzothiazol-3-one Chemical compound C1=CC=C2C(=O)N(CCCC)SC2=C1 LUYIHWDYPAZCNN-UHFFFAOYSA-N 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000001720 action spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 230000000857 drug effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
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- 239000004005 microsphere Substances 0.000 description 1
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- 229920001558 organosilicon polymer Polymers 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine and a preparation method thereof. The invention comprises the following raw materials: 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene, 14-20 parts of glass fiber material, 0.5-1 part of coupling agent, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch; the antibacterial and mildewproof master batch comprises the following components: 75-85 parts of polypropylene, 15-25 parts of composite antibacterial agent, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent and 0.5-1.0 part of lubricant; the composite antibacterial agent is a mixture of zinc pyrithione and thiazole antibacterial agent. The polypropylene is added with the antibacterial and mildewproof master batch containing the composite antibacterial agent, so that the outer barrel of the washing machine meets the requirements of the washing machine on the mechanical, ageing-resistant and antibacterial and mildewproof properties of the outer barrel material, is washing-resistant, and the antibacterial and mildewproof properties are basically unchanged after multiple times of washing.
Description
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and particularly relates to antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine and a preparation method thereof.
Background
Plastic products are ubiquitous in our lives and are widely used in various fields of life, such as household appliances, kitchens and bathrooms, medical treatment, food and the like. But the plastic products are easily infected with bacteria, and especially, the additives added in the processing process of the plastic products are a nutrient source for breeding bacteria and are easy to breed the bacteria; if not controlled, the bacteria will multiply in large quantities, even bring about the infection of diseases, thereby bringing about the threat to the health of people. At present, plastic products in many fields have antibacterial effect and are widely used in human life, for example: an antibacterial toilet lid, an antibacterial fabric, an antibacterial water pipe, an antibacterial air conditioner filter screen and the like. But the antibiosis is different from sterilization, and the antibiosis material only protects the material from being corroded and damaged by bacteria, improves the service life, does not become a propagation source of the bacteria, does not damage the environment and does not threaten the human health.
The drum washing machine is an indispensable household appliance in family life, and people also put forward more rigorous requirements on the performance of the drum washing machine, and the drum washing machine is required to be more sanitary and clean on the basis of requiring higher rotating speed and higher mechanical property. In the process of finishing washing and draining water of the drum washing machine, a large amount of impurities remain between the inner drum and the outer drum, and the impurities become nutrient substances for breeding bacteria. Since the inner barrel is generally made of stainless steel material and the outer barrel is generally made of polypropylene material, bacteria are more easily proliferated on the polypropylene material of the outer barrel. After the use time is longer, the service life of the outer barrel can be shortened due to the mass propagation of bacteria and mold, and the bacteria can cause secondary pollution and be stained on clothes, so that great threat is brought to the health of people.
Therefore, the outer barrel of the drum washing machine is necessary to be modified for antibiosis and mildew resistance, so that the service life of the washing machine can be prolonged, and the health of consumers can be ensured. Some antibacterial polypropylene composites for washing machine drums have appeared in the prior art, such as: chinese patent CN108003465A discloses an antibacterial modified long glass fiber reinforced polypropylene composite material for a washing machine roller, which is a polypropylene composite material with excellent comprehensive performance and can reach various performance indexes required by the roller of a highly-configured roller washing machine; however, the polypropylene composite material adopts the biguanide antibacterial agent or the dihydroxyl antibacterial agent, so that the polypropylene composite material has poor washing fastness, the antibacterial effect of the polypropylene composite material is obviously reduced after multiple times of washing, and the polypropylene composite material only has the antibacterial performance and cannot meet the requirement of the mildew-proof performance, so that the polypropylene composite material cannot be popularized and applied in the field of outer barrels of drum washing machines on a large scale.
Disclosure of Invention
The invention provides antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine and a preparation method thereof, and solves the problems that in the prior art, a polypropylene composite material for a drum of the washing machine has poor washing fastness, and the antibacterial and mildewproof effect is obviously reduced after multiple times of washing.
The invention discloses antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which is mainly realized by the following technical scheme: the feed comprises the following raw materials in parts by weight: 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene, 14-20 parts of glass fiber material, 0.5-1 part of coupling agent, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch; the antibacterial and mildewproof master batch comprises the following components in parts by weight: 75-85 parts of polypropylene, 15-25 parts of composite antibacterial mildew preventive, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent and 0.5-1.0 part of lubricant; the composite antibacterial mildew preventive is a mixture of zinc pyrithione and thiazole antibacterial agents according to the weight ratio of 2:1-4: 1.
The invention adds the antibacterial and mildewproof master batch containing the composite antibacterial and mildewproof agent into polypropylene, wherein the composite antibacterial and mildewproof agent is a mixture consisting of an organic zinc antibacterial agent, namely zinc pyrithione and thiazole antibacterial agents; the organic zinc antibacterial agent in the composite antibacterial mildew inhibitor has double effects of antibiosis and mildew resistance, the antibacterial effect is superior to the mildew resistance, the Minimum Inhibitory Concentration (MIC) of mildew resistance is far greater than the Minimum Inhibitory Concentration (MIC) of the antibiosis, after repeated washing loss, the content of the organic zinc antibacterial agent is partially lost, but the minimum inhibitory concentration of the organic zinc antibacterial agent to bacteria is very low, the organic zinc antibacterial agent still has enough components for inhibiting the growth of the bacteria and has excellent antibacterial effect, and at the moment, the mildew resistance is reduced due to insufficient quantity of mildew inhibition; the thiazole antibacterial agent also has double effects of antibiosis and mildew prevention, the mildew prevention effect is more excellent, the Minimum Inhibitory Concentration (MIC) of mildew prevention is very low, the slow release effect is very strong, the mildew prevention effect is lasting, and the thiazole antibacterial agent still has good mildew prevention effect after being washed for many times; after the organic zinc antibacterial agent and the thiazole antibacterial agent are compounded, the organic zinc antibacterial agent and the thiazole antibacterial agent supplement each other and promote each other, and still have good antibacterial and mildewproof effects after being washed at high temperature for many times. When the antibacterial and mildewproof polypropylene prepared from the antibacterial and mildewproof master batch containing the composite antibacterial and mildewproof agent is used for the outer barrel of the washing machine, the breeding and propagation of bacteria and mildews on the surface of the outer barrel can be effectively inhibited, and the antibacterial and mildewproof polypropylene still has good antibacterial and mildewproof effects after long-time washing; meanwhile, the antibacterial and mildewproof polypropylene also has the advantages of high strength, high rigidity, excellent dimensional stability, impact resistance and the like, and meets the requirements of the drum washing machine on the mechanical property and the aging resistance of the outer barrel polypropylene material.
In a preferred embodiment, the thiazole antibacterial and antifungal agent is any one or more of DCOIT, OIT and BBIT. The zinc pyrithione is also called bis (2-sulfo-1-pyridine oxide) zinc, abbreviated as ZPT, is a low-toxicity, high-efficiency and environment-friendly antibacterial and mildewproof agent, and has good inhibition effect on bacteria and fungi; DCOIT, named 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one in Chinese, a broad-spectrum antibacterial and mildewproof agent, a latest slow release technology, provides lasting protection, achieves or even exceeds the effect of TBTO (tributyltin compound), does not contain heavy metals, is released into the environment, quickly permeates into precipitates and is decomposed without accumulation; OIT, the Chinese name of 2-n-octyl-4-isothiazoline-3-ketone, has broad-spectrum sterilization, is mildew-proof and algae-resistant, does not contain mercury and lead, is green and environment-friendly, has low solubility in water and long drug effect time, and particularly has excellent control capability on mildew; BBIT, the Chinese name 2-butyl-1, 2-benzisothiazolin-3-one, is a new generation of BIT alkyl derivative, solves the problems existing in the use of BIT at present, such as low efficiency, large dosage, poor effect on mildew and algae, lack of microbial action spectrum and the like, has obtained American EPA authentication, and is environment-friendly and safe.
As a preferred embodiment, the compound antibacterial and antifungal agent is a mixture consisting of ZPT, DCOIT and OIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT and BBIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT, BBIT and OIT in a weight ratio of 3:0.7-0.8:0.1-0.2: 0.1-0.2. In the invention, ZPT and DCOIT are powder, OIT and BBIT are liquid, polypropylene is solid particles, and the compounding mode of the powder mildew preventive and the liquid mildew preventive is used, so that the compound antibacterial and mildew-proof effect can be met, a layer of liquid mildew preventive can be coated on the surface of the powder mildew preventive, the powder mildew preventive is promoted to be adhered to particles of a polypropylene base material, the compatibility of the powder mildew preventive and the polypropylene base material is improved, the granulation is more uniform, and the antibacterial and mildew-proof effect is better.
In a preferred embodiment, the glass fiber material is alkali-free long glass fiber with the fiber diameter of 8-10 μm, and the glass fiber material is modified by a silane coupling agent. The glass fiber is fibrous glass, has high mechanical strength, and grows along the inside of a polypropylene machine body when added into polypropylene, and the growth direction is consistent with the polypropylene crystallization direction; when external force acts on the polypropylene, the external force is further dispersed on the glass fiber, so that the effects of resisting the external force and improving the mechanical property of the polypropylene are achieved; in general, such alkali-free long glass fibers need to be completely uniformly impregnated in a silane coupling agent in advance.
In the polypropylene material, the addition amount of the antibacterial agent cannot be too high, and the too high addition amount of the antibacterial agent not only influences the manufacturing cost of the material, but also has great influence on the strength, rigidity, dimensional stability and impact resistance of the material, so that the mechanical property of the material is obviously reduced; meanwhile, the addition amount of the antibacterial agent cannot be too small, and because the consumption of the base material polypropylene in the polypropylene material is large, the too small antibacterial agent cannot be well dispersed in the polypropylene base material and cannot be fully and uniformly blended into the polypropylene base material, so that the antibacterial and mildew-proof performance of the obtained polypropylene material is influenced.
As a preferred embodiment, the polypropylene is a mixture of copolymerized polypropylene and homopolymerized polypropylene according to the weight ratio of 1:1-1.5:1, the melt index of the copolymerized polypropylene is 0.3-1.5g/10min, and the melt index of the homopolymerized polypropylene is 50-60g/10 min. The invention adopts the compounding of the low-melting-index co-polypropylene and the high-rigidity homo-polypropylene, the co-polypropylene has higher impact strength, but lower tensile strength, bending strength and modulus, the homo-polypropylene has higher rigidity, the strength and modulus of the co-polypropylene can be well improved, and the performances of the two raw materials are mutually synergistic.
As a preferred embodiment, the maleic anhydride grafted polypropylene has a grafting ratio of 1 to 1.6%. The maleic anhydride grafted polypropylene mainly has the effect of improving the compatibility of the polypropylene base material and the long glass fiber material, and the maleic anhydride grafted polypropylene provides polar groups for the polypropylene, and is combined with the silane coupling modified long glass fiber material through functional groups, so that the compatibility between the polypropylene base material and the long glass fiber material is improved.
The impact resistance of the polypropylene material is changed along with the change of the addition of the antibacterial mildew preventive, the composite antibacterial mildew preventive can improve the overall mechanical property of the polypropylene material, mainly because the composite antibacterial mildew preventive has small molecules, and the micromolecular composite antibacterial mildew preventive can improve the compatibility of the glass fiber material and the polypropylene base material due to the specific functional group contained in the micromolecular composite antibacterial mildew preventive on the basis of meeting the antibacterial mildew preventive effect of the polypropylene material, so that the glass fiber material is better dispersed in the polypropylene base material, and has better mechanical property; and the organic micromolecule composite antibacterial mildew inhibitor can also improve the fluidity of the polypropylene material, is beneficial to the dispersibility of the polypropylene material, is convenient for later processing and manufacturing, and improves the mechanical property and the dimensional stability of a product (such as an outer barrel of a drum washing machine) obtained by the organic micromolecule composite antibacterial mildew inhibitor.
As a preferred embodiment, the coupling agent is any one or more of silicone powder, KH-570, KH-550, KH-560 and KH 792. KH-550 belongs to aminosilane, mainly used for surface treatment of inorganic fillers, such as calcium carbonate, and also used for surface treatment of glass fiber; KH-560 belongs to epoxy silane, and is mainly used for surface treatment of reinforcing agent and inorganic filler, such as talcum powder, pottery clay, quartz, aluminum hydroxide, mica, glass microsphere, wollastonite, white carbon black, etc.; KH-570 belongs to methacryloxy functional group silane and is mainly used for treating glass fibers and improving the strength of products; KH792 belongs to aminosilane, which is used for coupling organic high polymer and inorganic substance to make them be chemically bonded into a whole; the silicone powder takes high molecular weight organosilicon polymer as main component, can improve the compatibility of non-polar inorganic mineral and organic interface, and can play a role in lubrication.
In a preferred embodiment, the lubricant is any one or more of PETS, EBS, polyethylene wax and calcium stearate. PETS, namely pentaerythritol stearate, is used as a common plastic additive, mainly plays a role of a lubricant and has good temperature resistance; EBS (ethylene bis stearamide) is an excellent lubricant and can effectively improve the flowability and the demolding property of a product; the PE wax, namely the polyethylene wax, is an excellent plastic lubricant, has good compatibility with polypropylene and strong internal lubrication; calcium stearate is a lubricant for various plastics, and has good lubricating effect and demoulding effect.
In a preferred embodiment, the oxidant is a mixture of oxidant 1010 and oxidant 168 in a weight ratio of 1: 1. Antioxidant 1010, which is a pentaerythritol ester, a phenolic antioxidant; the antioxidant 168 belongs to phosphite antioxidant, and can obtain better antioxidant effect by compounding with the antioxidant 1010.
The invention relates to a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which is mainly realized by the following technical scheme: the method comprises the following steps: 1) mixing zinc pyrithione and thiazole antibacterial agent according to the weight ratio of 2:1-4:1 to prepare a composite antibacterial mildew preventive for later use; 2) mixing 75-85 parts of polypropylene, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent, 0.5-1.0 part of lubricant and 15-25 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use; 3) mixing 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene and 0.5-1 part of coupling agent, adding 0.5-1 part of antioxidant and 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch obtained in the step 2), and uniformly mixing to obtain a mixture; 4) adding the mixture obtained in the step 3) into a double-screw extruder, adding 14-20 parts of long glass fiber material at a side feeding position, extruding, wherein the rotating speed of a main machine of the extruder is 310-340r/min, the main feeding rotating speed is 12-15r/min, the side feeding rotating speed is 2-4r/min, and the temperature of each of ten zones is as follows: the antibacterial and mildewproof polypropylene is obtained by cooling and granulating at the temperature of 180 ℃ in the first area, 185 ℃ in the second area, 200 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 210 ℃ in the seventh area, 220 ℃ in the seventh area, 210 ℃ in the eighth area, 220 ℃ in the ninth area, 220 ℃ in the tenth area, 215 ℃ in the tenth area and 220 ℃ in the head temperature of 215 ℃ in the first area, and cooling and granulating.
The preparation method of the antibacterial and mildewproof polypropylene comprises the steps of firstly preparing the composite antibacterial and mildewproof agent, then preparing the antibacterial and mildewproof master batch, finally adding the antioxidant, the lubricant and the antibacterial and mildewproof master batch into a mixture of the polypropylene, the maleic anhydride grafted polypropylene and the coupling agent, adding the long glass fiber material from a natural exhaust port, namely a side feeding port, and obtaining the antibacterial and mildewproof polypropylene through melt co-extrusion, cooling and granulation; the preparation method disclosed by the invention is simple, has no special requirements on equipment, is convenient to control, has low cost and is easy to industrialize, all the raw materials are fully mixed and melted by controlling the adding sequence of the materials, the raw materials are uniformly mixed, the influence of high temperature on the performances of the raw materials is avoided, the effects of all the raw materials are exerted to the greatest extent, the mechanical property and the anti-aging property of the antibacterial and mildewproof polypropylene are greatly improved, the requirements of a drum washing machine on an outer barrel polypropylene material are met, meanwhile, the antibacterial and mildewproof effect is high-efficiency and durable, the antibacterial and mildewproof performance is still good after multiple times of high-temperature washing, the breeding and propagation of bacteria and mildews on the surface of the outer barrel are effectively inhibited, and the secondary pollution is avoided.
Compared with the prior art, the invention has the beneficial effects that: the invention adds the antibacterial and mildewproof master batch containing the composite antibacterial and mildewproof agent into polypropylene, wherein the composite antibacterial and mildewproof agent is a mixture consisting of an organic zinc antibacterial agent, namely zinc pyrithione and thiazole antibacterial agents; the composite antibacterial mildew-proof agent, polypropylene, an antioxidant, a coupling agent and a lubricant are prepared into composite antibacterial mildew-proof master batch, then the composite antibacterial mildew-proof master batch is added into polypropylene and maleic anhydride grafted polypropylene, and under the auxiliary action of a glass fiber material, the coupling agent, the antioxidant and the lubricant, the raw materials supplement each other and are mutually promoted, the obtained antibacterial mildew-proof polypropylene can be used for an outer barrel of a washing machine to effectively inhibit breeding and propagation of bacteria and mildew on the surface of the outer barrel, and still has good antibacterial mildew-proof effect after long-time washing; meanwhile, the antibacterial and mildewproof polypropylene also has the advantages of high strength, high rigidity, excellent dimensional stability, impact resistance and the like, and meets the requirements of the drum washing machine on the mechanical property and the aging resistance of the outer barrel polypropylene material. The preparation method of the invention is simple, has no special requirements on equipment, is convenient to control, has low cost and is easy to industrialize.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following raw materials in parts by weight: 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene, 14-20 parts of glass fiber material, 0.5-1 part of coupling agent, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch; the antibacterial and mildewproof master batch comprises the following components in parts by weight: 75-85 parts of polypropylene, 15-25 parts of composite antibacterial mildew preventive, 0.5-0.8 part of antioxidant, 0.3-0.6 part of polysiloxane coupling agent and 0.5-1.0 part of lubricant; the composite antibacterial mildew preventive is a mixture of zinc pyrithione and thiazole antibacterial agents according to the weight ratio of 2:1-4: 1.
Preferably, the thiazole antibacterial and mildewproof agent is any one or more of DCOIT, OIT and BBIT.
Further, the compound antibacterial and antifungal agent is a mixture consisting of ZPT, DCOIT and OIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT and BBIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT, BBIT and OIT in a weight ratio of 3:0.7-0.8:0.1-0.2: 0.1-0.2.
Specifically, the glass fiber material is alkali-free long glass fiber, the fiber diameter is 8-10 μm, and the glass fiber material is modified by a silane coupling agent.
More preferably, the polypropylene is a mixture of copolymerized polypropylene and homopolymerized polypropylene according to the weight ratio of 1:1-1.5:1, the melt index of the copolymerized polypropylene is 0.3-1.5g/10min, and the melt index of the homopolymerized polypropylene is 50-60g/10 min.
Further, the maleic anhydride grafted polypropylene has a grafting ratio of 1-1.6%.
More specifically, the coupling agent is any one or more of silicone powder, KH-570, KH-550, KH-560 and KH 792.
Preferably, the lubricant is one or more of PETS, EBS, polyethylene wax and calcium stearate.
Still further, the oxidant is a mixture of oxidant 1010 and oxidant 168 in a weight ratio of 1: 1.
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) mixing zinc pyrithione and thiazole antibacterial agent according to the weight ratio of 2:1-4:1 to prepare a composite antibacterial mildew preventive for later use;
2) mixing 75-85 parts of polypropylene, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent, 0.5-1.0 part of lubricant and 15-25 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use;
3) mixing 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene and 0.5-1 part of coupling agent, adding 0.5-1 part of antioxidant and 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch obtained in the step 2), and uniformly mixing to obtain a mixture;
4) adding the mixture obtained in the step 3) into a double-screw extruder, adding 14-20 parts of long glass fiber material at a side feeding position, extruding, wherein the rotating speed of a main machine of the extruder is 310-340r/min, the main feeding rotating speed is 12-15r/min, the side feeding rotating speed is 2-4r/min, and the temperature of each of ten zones is as follows: the antibacterial and mildewproof polypropylene is obtained by cooling and granulating at the temperature of 180 ℃ in the first area, 185 ℃ in the second area, 200 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 210 ℃ in the seventh area, 220 ℃ in the seventh area, 210 ℃ in the eighth area, 220 ℃ in the ninth area, 220 ℃ in the tenth area, 215 ℃ in the tenth area and 220 ℃ in the head temperature of 215 ℃ in the first area, and cooling and granulating.
Example one
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) mixing ZPT, DCOIT and BBIT at a weight ratio of 4:0.8:0.2 to obtain composite antibacterial mildew inhibitor;
2) taking a mixture of the copolymer polypropylene and the homopolymerized polypropylene according to the weight ratio of 1:1 to obtain the composite polypropylene, wherein the melt index of the copolymer polypropylene is 0.3g/10min, and the melt index of the homopolymerized polypropylene is 54g/10 min;
taking an oxidant 1010 and an oxidant 168, and forming a mixture according to the weight ratio of 1:1 to obtain a composite oxidant;
3) mixing 80 parts of the composite polypropylene obtained in the step 2), 0.5 part of composite antioxidant, 0.5 part of coupling agent silicone powder, 0.5 part of lubricant PETS and 20 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use;
4) adding 78 parts of the polypropylene obtained in the step 2), 3 parts of maleic anhydride grafted polypropylene with the grafting rate of 1.4 percent and 0.5 part of coupling agent silicone powder into a high-speed mixer for preliminary mixing and mixing, adding 0.6 part of the composite antioxidant obtained in the step 2), 0.5 part of the lubricant PETS and 4 parts of the antibacterial and mildewproof master batch obtained in the step 3), blending and uniformly mixing to obtain a mixture;
5) adding the mixture obtained in the step 4) into a storage hopper of a double-screw extruder, adding 15 parts of long glass fiber material from a natural exhaust port, and extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, the side feeding speed is 4r/min, and the temperatures of ten zones are respectively: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head temperature, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene;
the glass fiber material of the embodiment is alkali-free long glass fiber, the fiber diameter is 9 μm, and the glass fiber material is modified by a silane coupling agent.
Example two
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) mixing an organic zinc antibacterial agent ZPT and a thiazole antibacterial agent DCOIT according to the weight ratio of 3:1 to prepare a composite antibacterial mildew preventive for later use;
2) mixing 80 parts of polypropylene, 0.5 part of antioxidant, 0.5 part of coupling agent, 0.5 part of lubricant and 20 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use;
3) adding 78 parts of polypropylene, 2 parts of maleic anhydride grafted polypropylene and 0.5 part of coupling agent into a high-speed mixer for preliminary mixing, adding 10100.3 parts of antioxidant, 1680.3 parts of antioxidant, 0.5 part of lubricant PETS and 3 parts of antibacterial and mildewproof master batch obtained in the step 2), blending uniformly, and obtaining a mixed material;
4) adding the mixture obtained in the step 3) into a storage hopper of a double-screw extruder, adding 17 parts of long glass fiber material from a natural exhaust port, and extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, and the temperatures of ten zones with the side feeding speed of 4r/min are respectively as follows: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene.
EXAMPLE III
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) mixing ZPT, DCOIT and OIT in a weight ratio of 2:0.8:0.2 to prepare the composite antibacterial mildew inhibitor for later use;
2) mixing 75 parts of polypropylene, 0.5 part of antioxidant, 0.3 part of coupling agent, 0.5 part of lubricant and 25 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batch for later use;
3) adding 75 parts of polypropylene, 3 parts of maleic anhydride grafted polypropylene and KH-5700.5 parts of coupling agent into a high-speed mixer for primary mixing, adding 10100.5 parts of antioxidant, 0.5 part of lubricant PETS and 2 parts of antibacterial and mildewproof master batch obtained in the step 2), blending, and uniformly mixing to obtain a mixed material;
4) adding the mixture obtained in the step 3) into a storage hopper of a double-screw extruder, adding 20 parts of long glass fiber material from a natural exhaust port, and extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, the side feeding speed is 4r/min, and the temperatures of ten zones are respectively: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene.
Example four
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) taking an organic zinc antibacterial agent ZPT, thiazole antibacterial agents DCOIT, OIT and BBIT, and mixing the raw materials according to the ratio of ZPT to DCOIT to OIT: mixing BBIT at a weight ratio of 2:0.8:0.1:01 to prepare a composite antibacterial mildew inhibitor for later use;
2) mixing 85 parts of polypropylene, 0.8 part of antioxidant, 0.6 part of coupling agent, 1.0 part of lubricant and 15 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use;
3) taking 77 parts of polypropylene, 3 parts of maleic anhydride grafted polypropylene and 1.0 part of coupling agent silicone powder, adding into a high-speed mixer for primary mixing, adding 10100.5 parts of antioxidant, 1680.5 part of antioxidant, 1.0 part of lubricant PETS and 6 parts of antibacterial and mildewproof master batch obtained in the step 2), blending, and uniformly mixing to obtain a mixed material;
4) adding the mixture obtained in the step 3) into a storage hopper of a double-screw extruder, adding 14 parts of long glass fiber material from a natural exhaust port, extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, the side feeding speed is 4r/min, and the temperatures of ten zones are respectively: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene.
EXAMPLE five
The invention discloses a preparation method of antibacterial and mildewproof polypropylene for an outer barrel of a drum washing machine, which comprises the following steps:
1) mixing ZPT, DCOIT and BBIT at a weight ratio of 3:0.8:0.2 to obtain composite antibacterial mildew inhibitor;
2) mixing 85 parts of polypropylene, 0.5 part of antioxidant, 0.5 part of coupling agent, 0.5 part of lubricant and 25 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use;
3) adding 79 parts of polypropylene, 3 parts of maleic anhydride grafted polypropylene and 0.5 part of coupling agent silicone powder into a high-speed mixer for primary mixing, adding 10100.3 parts of antioxidant, 1680.3 parts of antioxidant, 0.5 part of lubricant PETS and 3 parts of the antibacterial and mildewproof master batch obtained in the step 2), blending, and uniformly mixing to obtain a mixed material;
4) adding the mixture obtained in the step 3) into a storage hopper of a double-screw extruder, adding 15 parts of long glass fiber material from a natural exhaust port, and extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, the side feeding speed is 4r/min, and the temperatures of ten zones are respectively: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene.
Comparative experiment 1
The preparation method of the antibacterial and mildewproof polypropylene comprises the following steps:
1) mixing 80 parts of polypropylene, 0.5 part of antioxidant, 0.5 part of coupling agent, 0.5 part of lubricant and 20 parts of antibacterial mildew preventive ZPT, and preparing into antibacterial mildew preventive master batch for later use;
2) adding 83 parts of polypropylene, 3 parts of maleic anhydride grafted polypropylene and KH-5700.5 parts of coupling agent into a high-speed mixer for primary mixing, adding 2 parts of the antibacterial and mildewproof master batch obtained in the step 1), blending, and uniformly mixing to obtain a mixture;
3) adding the mixture obtained in the step 2) into a storage hopper of a double-screw extruder, adding 12 parts of long glass fiber material from a natural exhaust port, and extruding, wherein the rotating speed of a main machine of the extruder is 320r/min, the main feeding rotating speed is 14r/min, the side feeding speed is 4r/min, and the temperatures of ten zones are respectively: 175 ℃ in the first area, 180 ℃ in the second area, 190 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 220 ℃ in the seventh area, 215 ℃ in the eighth area, 215 ℃ in the ninth area, 215 ℃ in the tenth area and 220 ℃ in the head, cooling the extruded material strips to the room temperature through a water tank, and granulating through a granulator to obtain the antibacterial and mildewproof polypropylene.
Comparative experiment 2
A glass fiber reinforced antibacterial mildewproof polypropylene material is purchased from the market, and the content of the glass fiber is 15.2 percent through ash analysis.
Five parts of the antibacterial and mildewproof polypropylene obtained in the first to fifth embodiments of the invention are used for an outer barrel of a drum washing machine, the antibacterial and mildewproof polypropylene material prepared in the first comparative experiment (namely, the first comparative sample) and the conventional antibacterial polypropylene material purchased in the second comparative experiment (namely, the second comparative sample) are respectively subjected to performance test experiments, wherein the performance tests comprise tensile strength, bending modulus, notched izod impact strength, antibacterial property and mildewproof property, the tensile strength is carried out according to a method specified by GB/T1040, the bending strength and the bending modulus are carried out according to a method specified by GB/T9341, the notched izod impact strength is carried out according to a method specified by GB/T1843, the antibacterial property and the mildewproof property are carried out according to a method specified by GB/T21551.2, and the experimental results are shown in Table 1.
TABLE 1 results of Performance testing of various polypropylenes
As can be seen from Table 1, the tensile strength of the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine is 75-90MPa, the bending strength is 100-112MPa, the bending modulus is 3400-4000MPa, and the notched impact strength of the cantilever beam is 14-16KJ/m2Therefore, the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine has good mechanical property; the antibacterial and mildew-proof polypropylene for the outer barrel of the drum washing machine has the antibacterial property of more than 99 percent and the mildew resistance of 0 grade, has good antibacterial and mildew-proof performance, and meets the use requirement of the outer barrel of the drum washing machine under the normal temperature condition. The mechanical property and the antibacterial and mildewproof property of the comparison sample I are close to those of the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine; although the antibacterial performance of the second control sample is relatively close to that of the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine, the mildewproof performance of the second control sample is far lower than that of the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine, the mechanical performance of the second control sample is far lower than that of the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine, and the mechanical performance, the antibacterial performance and the mildewproof performance of the second control sample cannot be considered at the same time.
Five parts of the antibacterial and mildewproof polypropylene obtained in the first to fifth embodiments of the invention and used for the outer barrel of the drum washing machine, the antibacterial and mildewproof polypropylene material prepared in the first comparative experiment (namely, the first comparative sample) and the existing antibacterial polypropylene material purchased in the second comparative experiment (namely, the second comparative sample) are respectively subjected to a boiling resistance test experiment, and the experimental method comprises the following steps: the antibacterial and mildewproof polypropylene material is respectively made into plastic sheets with the size of 5cm multiplied by 5cm, the plastic sheets are respectively soaked in warm water with the temperature of 90 ℃ for different time, namely, the first stage 800h, the second stage 1600h, the third stage 2400h and the fourth stage 3200h, after the soaking is finished, the plastic sheets are dried at normal temperature without surface wiping, then the test experiments of the tensile strength, the bending modulus, the cantilever beam notch impact strength, the antibacterial property and the mildewproof property are carried out, and the test results are shown in tables 2 to 5.
As can be seen from tables 2 to 5, the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine has reduced mechanical properties after water aging, but the mechanical properties of the polypropylene do not change much after the time is continuously prolonged, and the mechanical properties of the polypropylene still can meet the mechanical property requirements of the outer barrel of the drum washing machine, which shows that the polypropylene has better mechanical stability. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine has antibacterial and mildewproof performance, and maintains good antibacterial and mildewproof effect along with the prolonging of the water aging time. Therefore, the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine can keep good antibacterial and mildewproof effects in the whole service life of the drum washing machine. However, the second control sample had substantially no anti-mold effect after 800h of water aging, so no subsequent aging test was performed; the polypropylene material of the first comparison sample has gradually reduced antibacterial and mildewproof performance after being aged by water, the mildewproof performance is reduced to 1 grade after being aged by water for 800 hours, and then the antibacterial performance of the first comparison sample is reduced to be more than 90 percent finally. Therefore, the antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine has obvious advantages in the water-aging resistant experiment process compared with the first control sample and the second control sample.
TABLE 2 different Polypropylene Performance test results (800h)
TABLE 3 different Polypropylene Performance test results (1600h)
TABLE 4 different Polypropylene Performance test results (2400h)
TABLE 5 different Polypropylene Performance test results (3200h)
Compared with the prior art, the invention has the beneficial effects that: the invention adds the antibacterial and mildewproof master batch containing the composite antibacterial and mildewproof agent into polypropylene, wherein the composite antibacterial and mildewproof agent is a mixture consisting of an organic zinc antibacterial agent, namely zinc pyrithione and thiazole antibacterial agents; the composite antibacterial mildew-proof agent, polypropylene, an antioxidant, a coupling agent and a lubricant are prepared into composite antibacterial mildew-proof master batch, then the composite antibacterial mildew-proof master batch is added into polypropylene and maleic anhydride grafted polypropylene, and under the auxiliary action of a glass fiber material, the coupling agent, the antioxidant and the lubricant, the raw materials supplement each other and are mutually promoted, the obtained antibacterial mildew-proof polypropylene can be used for an outer barrel of a washing machine to effectively inhibit breeding and propagation of bacteria and mildew on the surface of the outer barrel, and still has good antibacterial mildew-proof effect after long-time washing; meanwhile, the antibacterial and mildewproof polypropylene also has the advantages of high strength, high rigidity, excellent dimensional stability, impact resistance and the like, and meets the requirements of the drum washing machine on the mechanical property and the aging resistance of the outer barrel polypropylene material. The preparation method of the invention is simple, has no special requirements on equipment, is convenient to control, has low cost and is easy to industrialize.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The utility model provides an antibiotic mould proof polypropylene for drum type washing machine outer bucket which characterized in that:
the antibacterial and mildewproof polypropylene comprises the following raw materials in parts by weight: 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene, 14-20 parts of glass fiber material, 0.5-1 part of coupling agent, 0.5-1 part of antioxidant, 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch, wherein the antibacterial and mildewproof master batch comprises the following components in parts by weight: 75-85 parts of polypropylene, 15-25 parts of composite antibacterial and mildewproof agent, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent and 0.5-1.0 part of lubricant, wherein the composite antibacterial and mildewproof agent is a mixture consisting of zinc pyrithione and thiazole antibacterial agent according to the weight ratio of 2:1-4:1, and the thiazole antibacterial agent is any one or more of DCOIT, OIT and BBIT;
the preparation method of the antibacterial and mildewproof polypropylene comprises the following steps: 1) mixing zinc pyrithione and thiazole antibacterial agent according to the weight ratio of 2:1-4:1 to prepare a composite antibacterial mildew preventive for later use; 2) mixing 75-85 parts of polypropylene, 0.5-0.8 part of antioxidant, 0.3-0.6 part of coupling agent, 0.5-1.0 part of lubricant and 15-25 parts of the composite antibacterial and mildewproof agent obtained in the step 1) to prepare antibacterial and mildewproof master batches for later use; 3) mixing 75-80 parts of polypropylene, 2-3 parts of maleic anhydride grafted polypropylene and 0.5-1 part of coupling agent, adding 0.5-1 part of antioxidant and 0.5-1 part of lubricant and 2-6 parts of antibacterial and mildewproof master batch obtained in the step 2), and uniformly mixing to obtain a mixture; 4) adding the mixture obtained in the step 3) into a double-screw extruder, adding 14-20 parts of long glass fiber material at a side feeding position, extruding, wherein the rotating speed of a main machine of the extruder is 310-340r/min, the main feeding rotating speed is 12-15r/min, the side feeding rotating speed is 2-4r/min, and the temperature of each of ten zones is as follows: the antibacterial and mildewproof polypropylene is obtained by cooling and granulating at the temperature of 180 ℃ in the first area, 185 ℃ in the second area, 200 ℃ in the third area, 205 ℃ in the fourth area, 210 ℃ in the fifth area, 210 ℃ in the sixth area, 210 ℃ in the seventh area, 220 ℃ in the seventh area, 210 ℃ in the eighth area, 220 ℃ in the ninth area, 220 ℃ in the tenth area, 215 ℃ in the tenth area and 220 ℃ in the head temperature of 215 ℃ in the first area, and cooling and granulating.
2. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the composite antibacterial and antifungal agent is a mixture consisting of ZPT, DCOIT and OIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT and BBIT in a weight ratio of 3:0.8:0.1-0.2, or a mixture consisting of ZPT, DCOIT, BBIT and OIT in a weight ratio of 3:0.7-0.8:0.1-0.2: 0.1-0.2.
3. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the glass fiber material is alkali-free long glass fiber, the diameter of the glass fiber is 8-10 mu m, and the glass fiber material is modified by a silane coupling agent.
4. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the polypropylene is a mixture of copolymerized polypropylene and homopolymerized polypropylene according to the weight ratio of 1:1-1.5:1, the melt index of the copolymerized polypropylene is 0.3-1.5g/10min, and the melt index of the homopolymerized polypropylene is 50-60g/10 min.
5. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the grafting rate of the maleic anhydride grafted polypropylene is 1-1.6%.
6. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the coupling agent is any one or more of KH-570, KH-550, KH-560 and KH 792.
7. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the lubricant is one or more of PETS, EBS, polyethylene wax and calcium stearate.
8. The antibacterial and mildewproof polypropylene for the outer barrel of the drum washing machine as claimed in claim 1, wherein:
the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 1: 1.
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| CN110819008A (en) * | 2019-12-06 | 2020-02-21 | 广东圆融新材料有限公司 | Easy-to-clean spray-free polypropylene material and preparation method thereof |
| CN111117076A (en) * | 2019-12-25 | 2020-05-08 | 界首市天路包装材料有限公司 | Special modified material with mildew-proof function for coating bucket |
| CN111499975A (en) * | 2020-05-12 | 2020-08-07 | 广东顺威赛特工程塑料开发有限公司 | Antibacterial and mildew-proof reinforced polypropylene composite material for fan blades and preparation method thereof |
| CN111645348A (en) * | 2020-06-09 | 2020-09-11 | 浙江吉利汽车研究院有限公司 | A kind of preparation method of air-conditioning air duct with antibacterial and antifungal properties |
| CN111972408A (en) * | 2020-08-20 | 2020-11-24 | 南京天诗蓝盾生物科技有限公司 | Special antibacterial mildew inhibitor for casein and preparation method thereof |
| CN112175301B (en) * | 2020-10-22 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Special antibacterial polypropylene material for washing machine and preparation method thereof |
| CN113337036B (en) * | 2021-04-21 | 2023-06-09 | 日丰企业集团有限公司 | Modified polypropylene material and preparation method thereof |
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