CN114213713B - Silane coupling agent modified halloysite nanotube-loaded antibacterial agent compound, polycarbonate composition, and preparation methods and applications thereof - Google Patents
Silane coupling agent modified halloysite nanotube-loaded antibacterial agent compound, polycarbonate composition, and preparation methods and applications thereof Download PDFInfo
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- CN114213713B CN114213713B CN202111342811.6A CN202111342811A CN114213713B CN 114213713 B CN114213713 B CN 114213713B CN 202111342811 A CN202111342811 A CN 202111342811A CN 114213713 B CN114213713 B CN 114213713B
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 61
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 61
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical class O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002071 nanotube Substances 0.000 title claims abstract description 53
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 77
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 46
- 239000003963 antioxidant agent Substances 0.000 claims description 31
- 230000003078 antioxidant effect Effects 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 230000000845 anti-microbial effect Effects 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
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- 239000000463 material Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004599 antimicrobial Substances 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 239000000022 bacteriostatic agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- AUEIOPXLEWSKBS-JTQLQIEISA-N 4-[(5s)-5-(acetamidomethyl)-2-oxo-1,3-oxazolidin-3-yl]-2-fluoro-n-methylbenzamide Chemical compound C1=C(F)C(C(=O)NC)=CC=C1N1C(=O)O[C@@H](CNC(C)=O)C1 AUEIOPXLEWSKBS-JTQLQIEISA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JPFSNUBRFGFBAR-UHFFFAOYSA-N N-[3-[1-[(4-methylphenyl)methyl]benzimidazol-2-yl]phenyl]methanesulfonamide Chemical compound CS(=O)(=O)NC1=CC(=CC=C1)C1=NC2=C(N1CC1=CC=C(C=C1)C)C=CC=C2 JPFSNUBRFGFBAR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
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- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000005469 granulation Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
-
- 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
- C08K2003/085—Copper
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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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)
Abstract
The invention relates to a halloysite nanotube-loaded antibacterial agent compound modified by a silane coupling agent, a polycarbonate composition, a preparation method and application thereof. The halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent has good short-acting antibacterial effect and long-acting antibacterial effect, and can be used as an antibacterial functional component to be added into a polycarbonate composition, so that the short-acting antibacterial performance and long-acting antibacterial performance of the polycarbonate composition can be effectively improved, and the halloysite nanotube-loaded antibacterial agent compound can be widely applied to the fields of automobiles, household appliances, consumer electronics, medical appliances and the like.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a halloysite nanotube-loaded antibacterial agent compound modified by a silane coupling agent, a polycarbonate composition, and a preparation method and application thereof.
Background
The polycarbonate is engineering plastic with excellent comprehensive performance, has good mechanical property, excellent impact toughness, thermal stability and the like, has good beautiful effect, high glossiness and the like, and has been widely applied to the fields of automobiles, household appliances, consumer electronics, medical appliances and the like. With the development of economy and the improvement of the living standard and health consciousness of people, consumers are also required to have higher demands on plastic products such as polycarbonate which are in contact with life, for example, to impart antibacterial properties.
Antibacterial plastics can be realized by adding antibacterial agents into plastics, so that bacteria, mold, saccharomycetes, algae, even viruses and the like on the surfaces of plastic products are inhibited or killed. Currently, the mainstream antibacterial polycarbonate materials on the market are mainly realized by adding an antibacterial agent to polycarbonate. Chinese patent CN107459802A discloses an antibacterial polycarbonate plastic, wherein a composite antibacterial agent which takes nano zinc oxide, nano silver oxide and organosilicon quaternary ammonium salt solution as main sterilization components and ceramic powder as a carrier is added, and the polycarbonate plastic of the patent has good antibacterial performance and mechanical performance by adding the composite antibacterial agent, but has insufficient antibacterial durability. Chinese patent CN111732825A discloses an antibacterial polycarbonate plastic, in which porous beads formed by crosslinking reaction of polystyrene butadiene copolymer and chloromethyl styrene are used as carriers to load nano zinc oxide and nano titanium dioxide as active components, but the porous beads in the patent have large pore diameter, the antibacterial agent is easy to separate out, the long-acting antibacterial effect is not obvious, and the antibacterial performance is obviously reduced (reduced by 7.5-12.5%) in a higher humidity or higher temperature environment.
Therefore, development of a polycarbonate material having long-term antibacterial properties has important research value.
Disclosure of Invention
The invention aims to overcome the defect or defect of poor long-term antibacterial performance of a polycarbonate material in the prior art and provides a halloysite nanotube-loaded antibacterial agent compound modified by a silane coupling agent. According to the invention, the halloysite nanotubes are used for loading the bacteriostat, and the silane coupling agent is used for modification, so that the dispersibility of the bacteriostat can be improved, the short-acting antibacterial effect can be effectively improved, and the long-acting antibacterial effect can be realized. The antibacterial composite can be added into the polycarbonate composition to effectively improve the short-acting antibacterial performance and the long-acting antibacterial performance of the polycarbonate composition, and can be widely applied to the fields of automobiles, household appliances, consumer electronics, medical appliances and the like.
The invention also aims to provide a preparation method of the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent.
It is another object of the present invention to provide a long-acting antimicrobial polycarbonate composition.
It is another object of the present invention to provide a method for preparing the above-mentioned long-acting antibacterial polycarbonate composition.
It is another object of the present invention to provide the use of the above-described long-acting antimicrobial polycarbonate composition for the preparation of automobiles, household appliances, consumer electronics, medical devices.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the weight ratio of the silane coupling agent to the halloysite nanotube-loaded antioxidant compound in the silane coupling agent-modified halloysite nanotube-loaded antibacterial compound is (0.01-0.1) 1; the weight ratio of the halloysite nanotube to the antibacterial agent is 100 (0.1-2).
The porous carrier (such as molecular sieve, diatomite, active carbon and other porous adsorption load materials) is used for carrying and modifying the antibacterial agent to improve the dispersibility of the antibacterial agent, but researches show that although the modification method can effectively improve the short-acting antibacterial effect, the problem that the long-acting antibacterial performance is poor due to precipitation of the antibacterial agent still exists, and the reason is probably that the antibacterial agent is easy to precipitate from a porous structure and cannot realize long-acting antibacterial.
Halloysite nanotubes are natural nanotubes formed by curling aluminum silicate clay sheets, and the outer wall of the halloysite nanotubes is tetrahedral SiO 4 A sheet layer having a small amount of silanol groups at the end of the tube; while the inner wall of the tube cavity is hexahedral AlO 6 And a sheet layer with a portion of the aluminum alcohol functional groups. Repeated researches show that the halloysite nanotubes are used for loading the bacteriostat, so that the dispersibility of the bacteriostat can be improved, and the short-acting antibacterial effect can be effectively improved. On one hand, the halloysite nanotube has a special structure with two open ends, which can effectively slow down precipitation of the bacteriostat, and on the other handThe silane coupling agent is used for coating modification treatment, so that migration and precipitation of the antibacterial agent in the material use process can be further synergistically slowed down, and a long-acting antibacterial effect is realized.
Preferably, the inner diameter of the halloysite nanotube in the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent is 10-20 nm.
Preferably, the silane coupling agent in the halloysite nanotube-loaded antibacterial agent compound is one or more of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide (Si 69), gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidoxypropyl trimethoxysilane (KH 560) or gamma-methacryloxypropyl trimethoxysilane (KH 570).
Preferably, the antibacterial agent in the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent is one or more of nano silver, nano copper or nano zinc oxide.
More preferably, the antimicrobial agent is nano silver.
More preferably, the average particle diameter of the antibacterial agent is 2 to 15nm, still more preferably 5 to 12nm.
Preferably, in the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent, the weight ratio of the halloysite nanotube to the antibacterial agent is 100 (0.4-1.5).
The preparation method of the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent comprises the following steps:
s1: dispersing an antibacterial agent in water, adding halloysite nanotubes for ultrasonic stirring treatment, drying under negative pressure, and drying and grinding to obtain a halloysite nanotube-loaded antioxidant compound;
s2: dispersing halloysite nanotube loaded antioxidant compound in an organic solvent, adding a silane coupling agent, stirring, filtering, washing, drying and grinding to obtain the halloysite nanotube loaded antioxidant compound.
More preferably, the organic solvent is absolute ethanol.
The long-acting antibacterial polycarbonate composition comprises the following components in parts by weight:
the antibacterial compound is the halloysite nanotube-loaded antibacterial compound.
Polycarbonates conventional in the art may be used in the present invention, and preferably, the polycarbonate is one or more of an aromatic polycarbonate or a silicone copolycarbonate.
More preferably, the aromatic polycarbonate is bisphenol a type polycarbonate.
More preferably, the silicone copolycarbonate is polydimethylsiloxane-bisphenol a polycarbonate.
More preferably, the polycarbonate is an aromatic polycarbonate having an average molecular weight of 20000 to 28000.
When the average molecular weight of the aromatic polycarbonate is within the above range, the mechanical strength is good and good moldability can be ensured.
The average molecular weight was measured by gel permeation chromatography under the following specific conditions: dichloromethane was used as solvent and the test temperature was 25 ℃.
Preferably, the antioxidant is a mixture of a main antioxidant and an auxiliary antioxidant, and the weight ratio of the main antioxidant to the auxiliary antioxidant is 1 (0.5-1.0).
More preferably, the primary antioxidant is a hindered phenol primary antioxidant, and the secondary antioxidant is a phosphite secondary antioxidant.
Further preferably, the hindered phenol primary antioxidant is n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
Further preferably, the phosphite co-antioxidant is tris (2, 4-di-t-butylphenyl) phosphite.
Preferably, the lubricant is one or more of carboxylate, paraffin or silicone.
Other adjuvants conventional in the art may be used in the present invention.
Preferably, the long-acting antimicrobial polycarbonate composition further comprises other auxiliary agents, wherein the other auxiliary agents are one or more of flame retardants, anti-dripping agents or toughening agents.
More preferably, the flame retardant is one or more of a bromine-antimony flame retardant or a sulfonate flame retardant.
Further preferably, the weight portion of the bromine-antimony flame retardant is 1-10.
Further preferably, the sulfonate flame retardant is 0.05 to 0.5 part by weight.
More preferably, the anti-drip agent is polytetrafluoroethylene; the weight portion of the anti-dripping agent is 0.5 to 1 portion.
Preferably, the toughening agent is one or more of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylic ester-glycidyl methacrylate terpolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer, acrylic toughening agent or acrylic-silicon rubber toughening agent; the weight portion of the toughening agent is 0.5-5 portions.
More preferably, the toughening agent is an acrylic-silicone rubber type toughening agent.
The preparation method of the long-acting antibacterial polycarbonate composition comprises the following steps: and uniformly mixing the polycarbonate, the antibacterial compound, the antioxidant, the lubricant and other auxiliary agents (if any) to obtain a mixture, and then melting, extruding and granulating the mixture to obtain the long-acting antibacterial polycarbonate composition.
Specifically, the preparation method of the long-acting antibacterial polycarbonate composition comprises the following steps:
s1: weighing polycarbonate, an antibacterial compound, a lubricant and other auxiliary agents (if any) according to the proportion, and stirring and blending in a high-speed mixer to obtain a premix;
s2: putting the premix in the step S1 into a double-screw extruder, melting, extruding and granulating to obtain the long-acting antibacterial polycarbonate composition; the length-diameter ratio of the screw in the double-screw extruder is 40-45:1, the temperature of the screw cylinder is 210-250 ℃, and the rotating speed of the screw is 500-600 rpm.
The application of the long-acting antibacterial polycarbonate composition in preparing automobiles, household appliances, consumer electronics and medical appliances is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the polycarbonate composition provided by the invention uses the halloysite nanotube-loaded antioxidant compound modified by the silane coupling agent as an antibacterial functional component, can effectively improve the short-acting antibacterial performance and the long-acting antibacterial performance of the polycarbonate composition, and can be widely applied to the fields of automobiles, household appliances, consumer electronics, medical appliances and the like.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The reagents selected for the examples and comparative examples of the present invention are described below:
polycarbonate (PC) 1:1300 10NP, aromatic polycarbonate, LG chemistry, average molecular weight 25000;
polycarbonate (PC) 2:7030, an aromatic polycarbonate, mitsubishi, japan, having an average molecular weight of 36000;
and (3) a main antioxidant: beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate n-stearyl alcohol, sanfeng chemical Co., ltd;
auxiliary antioxidant: tris (2, 4-di-t-butylphenyl) phosphite, sanfeng chemical Co., ltd;
the antioxidant is prepared by compounding a main antioxidant and an auxiliary antioxidant according to the weight ratio of 1:1.
Silane coupling agent 1: si69, michelin reagent Co;
silane coupling agent 2: KH560, michelin reagents inc;
halloysite nanotube 1: a hollow tubular structure with an inner diameter of 10-20nm, and a production area of Hubei;
halloysite nanotube 2: a hollow tubular structure with an inner diameter of 18-25nm, and a production area of Hubei;
diatomaceous earth: porous structure, K812243, micin reagents, inc;
antimicrobial agent 1: nano silver with an average particle size of 10nm, available from Albumin Biochemical technologies Co., ltd;
antimicrobial agent 2: nano silver with average grain size of 2nm and Alasdine Biochemical technology Co., ltd;
antimicrobial agent 3: nano silver with average grain size of 15nm and manufactured by Allatin Biochemical technologies Co., ltd;
antibacterial agent 4: nano copper with an average particle size of 10nm, available from Albumin Biochemical technologies Co., ltd;
antibacterial agent 5: nano silver with average particle diameter of 20nm, available from Allatin Biochemical technologies Co., ltd;
the antibacterial composite 1-11 is self-made, wherein the antibacterial composite 1-9 is a halloysite nanotube-loaded antibacterial composite modified by a silane coupling agent, and the preparation method comprises the following steps: dispersing the antibacterial agent in water by stirring, adding halloysite nanotubes, carrying out ultrasonic stirring treatment for 1h, then placing the mixture in a vacuum oven at 50 ℃ for negative pressure drying, grinding and sieving, then adding the mixture into absolute ethyl alcohol, dropwise adding a silane coupling agent under the stirring condition of 500rpm, continuously stirring for 1h, standing, carrying out suction filtration, washing with absolute ethyl alcohol for two times, drying, grinding and sieving to obtain an antibacterial compound; the antibacterial compound 10 is halloysite nanotube-loaded antioxidant compound which is not modified by a silane coupling agent, and the preparation method is as follows: dispersing the antibacterial agent in water by stirring, adding halloysite nanotubes, performing ultrasonic stirring treatment for 1h, then placing into a vacuum oven at 50 ℃ for negative pressure drying, grinding and sieving to obtain an antibacterial compound; the antibacterial compound 11 is a diatomite loaded antibacterial compound modified by a silane coupling agent, and the preparation method is the same as the antibacterial compound 1# except that the halloysite nanotube is replaced by diatomite.
The amounts of the materials used are shown in Table 1.
TABLE 1 amounts (parts) of raw materials used in antimicrobial compositions 1 to 10
And (3) a lubricant: PETS, hair based chemicals limited;
toughening agent: s-2001, mitsubishi corporation of Japan.
The polycarbonate compositions of the examples and comparative examples of the present invention were prepared by the following procedure:
weighing the components according to a formula, premixing in a high-speed mixer to obtain premix, putting the premix into a double-screw extruder, carrying out melt mixing and extrusion granulation in the double-screw extruder to obtain the polycarbonate composition, wherein the length-diameter ratio of a screw is 45:1, and the temperatures of all zones of a screw barrel are 220 ℃, 240 ℃, 250 ℃, 260 ℃, 265 ℃, 275 ℃ and the screw rotation speed is 550rpm in sequence.
The test methods for the properties of the polycarbonate compositions provided in the examples and comparative examples of the present invention are as follows:
antibacterial performance test: short-acting antibacterial performance test refers to GB/T31402-2015 standard test; the antibacterial plate to be tested (obtained by injection molding of the polycarbonate compositions of each example and comparative example) is subjected to heat treatment in an oven at 80 ℃ for 168 hours, then is continuously treated in a double-85 (85 ℃/85%RH) humid heat aging oven for 168 hours, and finally is tested by referring to the GB/T31402-2015 standard, and the obtained antibacterial rate is the long-acting antibacterial rate.
Examples 1 to 15
This example provides a series of polycarbonate compositions whose formulations are shown in Table 1 in parts by weight.
TABLE 1 weight parts of the components in the formulations of examples 1-15 and results of the performance test
Comparative examples 1 to 5
This comparative example provides a series of polycarbonate compositions whose formulations are shown in Table 2 in parts by weight.
Table 2 results of the test of the parts by weight (parts) and the properties of the components in the formulations of comparative examples 1 to 5
The polycarbonate compositions provided in the examples and comparative examples were tested for their properties according to the performance test methods described above, and the results are shown in tables 1 and 2.
From the above test results, it is understood that the polycarbonate compositions provided in examples 1 to 15 have excellent short-acting antibacterial effect and long-acting antibacterial effect, and have high antibacterial retention. The increase in the amount of the antibacterial compound in example 13, example 1 and example 14, the short-acting antibacterial rate of the polycarbonate composition is basically consistent, but the long-acting antibacterial rate is improved, wherein the addition amount of the antibacterial compound in example 1 is moderate, the balance of cost and performance can be achieved, and the comprehensive performance is optimal. In comparative example 1, the antibacterial agent is directly added, the short-acting antibacterial rate is reduced, and the long-acting antibacterial rate is obviously reduced; the comparative example 2 further increases the dosage of the bacteriostatic agent, the short-acting antibacterial rate reaches 99.9%, but the long-acting antibacterial rate is still less than 70%; comparative example 3 in which the bacteriostatic agent, halloysite nanotube and silane coupling agent were directly added without prior loading and modification, the long-acting antibacterial rate was significantly reduced as compared with example 1; in comparative example 4, halloysite nanotube-loaded antioxidant compound which is not modified by a silane coupling agent is added as an antibacterial compound, the short-acting antibacterial rate is basically similar, but the long-acting antibacterial rate is reduced to a certain extent; in comparative example 5, the antioxidant is supported by diatomite, so that the short-acting antibacterial rate is high, but the long-acting antibacterial rate is poor.
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (10)
1. The halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent is characterized in that the weight ratio of the silane coupling agent to the halloysite nanotube-loaded antibacterial agent compound in the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent is (0.01-0.1) 1; the weight ratio of the halloysite nanotube to the antibacterial agent is 100 (0.1-2); the halloysite nanotube-loaded antibacterial agent compound modified by the silane coupling agent is a halloysite nanotube-loaded antibacterial agent compound coated by the silane coupling agent; the average grain diameter of the antibacterial agent is 2-15 nm.
2. The silane coupling agent modified halloysite nanotube-supported antibacterial agent complex according to claim 1, wherein the inner diameter of the halloysite nanotube is 10-20 nm.
3. The silane coupling agent modified halloysite nanotube-loaded antibacterial agent composite according to claim 1, wherein the antibacterial agent is one or more of nano silver, nano copper or nano zinc oxide.
4. The silane coupling agent modified halloysite nanotube-loaded antibacterial agent composite according to claim 1, wherein the silane coupling agent is one or more of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
5. The preparation method of the silane coupling agent modified halloysite nanotube-loaded antibacterial agent compound according to any one of claims 1 to 4, which is characterized by comprising the following steps:
s1: dispersing an antibacterial agent in water, adding halloysite nanotubes for ultrasonic stirring treatment, drying under negative pressure, and drying and grinding to obtain a halloysite nanotube-loaded antibacterial agent compound;
s2: dispersing halloysite nanotube-loaded antibacterial agent compound in an organic solvent, adding a silane coupling agent, stirring, filtering, washing, drying and grinding to obtain the product.
6. The long-acting antibacterial polycarbonate composition is characterized by comprising the following components in parts by weight:
the antibacterial compound is a halloysite nanotube-loaded antibacterial compound modified by the silane coupling agent according to any one of claims 1 to 4.
7. The long-acting antimicrobial polycarbonate composition of claim 1, wherein the polycarbonate is one or more of an aromatic polycarbonate or a silicone copolycarbonate.
8. The long-acting antimicrobial polycarbonate composition according to claim 1, wherein the antioxidant is a mixture of a primary antioxidant and a secondary antioxidant, the weight ratio of the primary antioxidant to the secondary antioxidant being 1 (0.5-1.0); the lubricant is one or more of carboxylate, paraffin or silicone.
9. A process for producing a long-acting antibacterial polycarbonate composition according to any one of claim 6 to 8, characterized in that,
the method comprises the following steps: and uniformly mixing the polycarbonate, the antibacterial compound, the antioxidant and the lubricant to obtain a mixture, and then melting, extruding and granulating the mixture to obtain the long-acting antibacterial polycarbonate composition.
10. Use of the long-acting antimicrobial polycarbonate composition according to any one of claims 6 to 8 for the preparation of automobiles, household appliances, consumer electronics, medical devices.
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| CN101999411A (en) * | 2010-11-17 | 2011-04-06 | 郑州大学 | Halloysite nano tube silver-carried monomer antibacterial agent and preparation method thereof |
| CN105107028A (en) * | 2015-08-17 | 2015-12-02 | 中国科学院长春应用化学研究所 | Medical material, preparation method of medical material and medical catheter made of medical material |
| CN109553949A (en) * | 2018-11-21 | 2019-04-02 | 金发科技股份有限公司 | A kind of antibacterial makrolon composite material and preparation method |
| CN110746654A (en) * | 2019-11-12 | 2020-02-04 | 华东理工大学 | Halloysite-containing flame-retardant antibacterial compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101999411A (en) * | 2010-11-17 | 2011-04-06 | 郑州大学 | Halloysite nano tube silver-carried monomer antibacterial agent and preparation method thereof |
| CN105107028A (en) * | 2015-08-17 | 2015-12-02 | 中国科学院长春应用化学研究所 | Medical material, preparation method of medical material and medical catheter made of medical material |
| CN109553949A (en) * | 2018-11-21 | 2019-04-02 | 金发科技股份有限公司 | A kind of antibacterial makrolon composite material and preparation method |
| CN110746654A (en) * | 2019-11-12 | 2020-02-04 | 华东理工大学 | Halloysite-containing flame-retardant antibacterial compound and preparation method thereof |
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