CN108774356A - A kind of preparation method of antibiotic plastic - Google Patents
A kind of preparation method of antibiotic plastic Download PDFInfo
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- CN108774356A CN108774356A CN201810626477.9A CN201810626477A CN108774356A CN 108774356 A CN108774356 A CN 108774356A CN 201810626477 A CN201810626477 A CN 201810626477A CN 108774356 A CN108774356 A CN 108774356A
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- Prior art keywords
- antibacterial
- preparation
- antibiotic plastic
- solution
- antibiotic
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- 229920003023 plastic Polymers 0.000 title claims abstract description 85
- 239000004033 plastic Substances 0.000 title claims abstract description 85
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000741 silica gel Substances 0.000 claims abstract description 29
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000000155 melt Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 58
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 29
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 29
- 239000004115 Sodium Silicate Substances 0.000 claims description 28
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 28
- -1 haloflex Polymers 0.000 claims description 24
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 241000894006 Bacteria Species 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- WGWACCCAJWZIML-UHFFFAOYSA-N benzene;buta-1,3-diene;prop-2-enenitrile Chemical group C=CC=C.C=CC#N.C1=CC=CC=C1 WGWACCCAJWZIML-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 abstract description 25
- 230000000845 anti-microbial effect Effects 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 7
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 75
- 239000000523 sample Substances 0.000 description 10
- 239000002609 medium Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000012496 blank sample Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 230000002421 anti-septic effect Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 235000015097 nutrients Nutrition 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 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 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- 241000235342 Saccharomycetes Species 0.000 description 2
- UFNRFBFHJJPDNF-UHFFFAOYSA-N [Zn].[Ce] Chemical compound [Zn].[Ce] UFNRFBFHJJPDNF-UHFFFAOYSA-N 0.000 description 2
- HIRUZABAEKUNEE-UHFFFAOYSA-N [Zn].[Ho] Chemical compound [Zn].[Ho] HIRUZABAEKUNEE-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical group C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- OTAYXVONQSYUEG-UHFFFAOYSA-N lutetium silver Chemical compound [Ag].[Lu] OTAYXVONQSYUEG-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- YSFHRHQJDPRCHZ-UHFFFAOYSA-N scandium silver Chemical compound [Sc].[Ag] YSFHRHQJDPRCHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2286—Oxides; Hydroxides of metals of silver
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention discloses a kind of preparation method of antibiotic plastic, antibacterial ion is supported on acquisition antimicrobial powder material on silica-gel carrier by this method by sol-gel method, it is used in combination silane coupling agent to be modified it, again by after modified antimicrobial powder and plastic substrate, antioxidant, plasticizer mixing, high concentration antibacterial matrices are melted, squeezed out, are granulated and to be obtained;Then it again by a certain percentage by itself and plastic substrate mixing, melts, squeeze out to obtain antibacterial sample；This method is modified by carrying out surface to antimicrobial powder and improves its dispersibility in plastic substrate, and the antibiotic plastic of preparation not only has that broad-spectrum antibacterial property, antibacterial timeliness be long, safe and plastics mechanical property does not change substantially.The fields such as household electrical appliances, packaging, kitchen and bath are can be widely used in, there is good application market foreground.
Description
Technical field
The invention discloses a kind of preparation methods of novel antibacterial plastics, more particularly to using silica gel as carrier, and will system
Standby antimicrobial powder is modified, and is had laid a good foundation to improve its dispersion performance in plastic substrate, to make
The anti-microbial property of antibiotic plastic is improved, and belongs to novel antibacterial plastic material technical field.
Background technology
There is a large amount of plastic products in daily life, as the shell and liner of household electrical appliance, kitchen and toilet facility,
Food packaging etc..Because plastics belong to organic macromolecule material, and other auxiliary agents can be added preparing link, in suitable condition
Under, it is very easy to make bacteria breed.People's lives are come into since antimicrobial product is more and more and are constantly approved by people, old friend
The plastic products frequently contacted in life are proposed with the new demand of " antibacterial, degerming ".
In terms of the development of recent domestic antibiotic plastic, answered as the antibacterial functions plastics of matrix using polypropylene, polyethylene
With widest in area, applied by multiple fields；The novel antibacterial plastic products of research and preparation with anti-microbial property, for changing
The living environment of philanthropists, the generation for reducing disease, environment purification etc. all have a very important significance.
Antiseptic includes organic antibacterial agent and inorganic antiseptic, wherein organic antibacterial agent have be more toxic, heat resistance compared with
Difference, the shortcomings of duration of efficacy is short；Inorganic antiseptic has many advantages, such as that heat-resist, antibacterial range is wide, the long event of antibacterial timeliness
It can be widely used in plastic products.
Invention content
The present invention is for antiseptic toxicity is big, drug resistance is poor, duration of efficacy is short and anti-in current antibacterial plastic product
Microbial inoculum mixes the problems such as uneven in plastic substrate, provides a kind of preparation method of antibiotic plastic, passes through sol-gel method
Antibacterial ion is supported on acquisition antimicrobial powder material on silica-gel carrier, is used in combination silane coupling agent to be modified it, optimization changes
Into dispersion performance of the antimicrobial powder in plastic substrate, then modified antimicrobial powder melted with plastic substrate, is blended, is squeezed
Go out, be granulated antibacterial matrices are made；Antibacterial modeling is made in antibacterial matrices and plastic substrate melt blending, extrusion by certain proportioning again
Expect sample；It being shown experimentally that, the antibiotic plastic sample prepared not only has many advantages, such as that broad-spectrum antibacterial property is strong, environment protection health,
And the mechanical property of plastics does not change substantially, therefore antibiotic plastic prepared by this method will have a good application prospect.
The method of the present invention carries out as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 70-90 DEG C are put by the ratio of 1.1-1.5
It in reactor, is reacted under the conditions of 70-90 DEG C of temperature, rotating speed 300-500r/min, silica gel is obtained after reacting 10-25min
Sol system；
（2）By volume 1:The ratio of 1.1-1.5 measures sodium silicate solution and sodium bicarbonate solution and is preheated to 70-90 respectively
DEG C, reactor rotating speed is then adjusted to 100-200r/min；Preheated sodium silicate solution and sodium bicarbonate solution are added successively
Enter step（1）Silica gel sol system in, obtain hi-sil system after fully reacting 15-30 min, add a concentration of 9 ×
10-5The metal ion solution of -1mol/L is adjusted with acid pH to 5-6, and the metal ion of addition is made to sink in the form of metal oxide
Product is on collosol and gel surface, the reaction was continued 0.5-3h, and reaction filters at once after stopping, and product is washed with deionized 2-3 times, then
It is washed 1-2 times with the modifier solution infiltration of mass concentration 1%-9%, is finally placed at 100-120 DEG C dry 1-3 h, taking-up is
Obtain antibacterial silica gel powder；
（3）Plastic substrate 80%-88%, antioxidant 1%-3%, plasticizer 1%-2%, step are weighed according to mass percent（2）It is anti-
Bacterium silica gel powder 10-15%；
（4）By step（3）Mixture is put into mixer, is taken out after melting mixing, and wherein mixer temperature in use is 170-
In 200 DEG C of mixers, rotor speed is 25-36 rpm；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, and mother particles of antibacterial plastics is made；
（6）Mother particles of antibacterial plastics 5%-10%, plastic substrate 90%-95% are sufficiently mixed by mass percentage, melts, squeeze out i.e.
Obtain antibiotic plastic.
The mass concentration of the sodium silicate solution is 5-15 %, and the mass concentration of sodium bicarbonate solution is 5-10%.
The metal ion solution is one kind in silver nitrate, zinc sulfate.
The modifying agent is one kind in KH550, KH560, KH570, KH151.
The antioxidant is one kind in antioxidant 1192, antioxidant 1010, antioxidant 1076.
The plasticizer is acrylonitrile-butadiene-styrene copolymer, haloflex, ethylene-vinyl acetate copolymerization
One kind in object.
The plastic substrate is one kind in the polypropylene of conventional commercial, polyethylene.
Rare earth ion salt can also be added in antibiotic plastic prepared by the present invention, i.e., in step（2）Middle addition metal ion
The rare earth ion salting liquid that concentration 0.001-1 mol/L are added after solution reaction 2-6min is adjusted with acid pH to 5-6, and the reaction was continued
Gel-like product, the wherein volume ratio 1 of metal ion solution and rare earth ion salting liquid are obtained after 0.5-3 h:1-3:1.
The rare earth ion salt is one kind in lanthanum nitrate, cerous nitrate, lutecium nitrate, yttrium nitrate, scandium nitrate, holmium nitrate.
It is as follows that the present invention prepares the advantages of antibiotic plastic method：
The present invention is for antiseptic toxicity is big, drug resistance is poor, duration of efficacy is short and antiseptic in current antibacterial plastic product
The problems such as uneven is mixed in plastic substrate, is provided a kind of preparation method of novel antibacterial plastics, is passed through sol-gel method
Antibacterial ion is supported on acquisition antimicrobial powder material on silica-gel carrier, is used in combination silane coupling agent to be modified it, optimization changes
Into dispersion performance of the antimicrobial powder in plastic substrate, then by modified antimicrobial powder and plastic substrate melt blending, squeeze
Go out, be granulated high concentration antibacterial matrices are made；Antibacterial matrices and plastic substrate melt blending, extrusion are made by certain proportioning again
Antibacterial sample；Experiment shows the antibiotic plastic prepared not only and has many advantages, such as that broad-spectrum antibacterial property is strong, environment protection health, but also moulds
The mechanical property of material does not change substantially, therefore studies and prepare the novel antibacterial plastic products with anti-microbial property, has good
Application prospect.
Specific implementation mode
Below by embodiment, invention is further described in detail, but protection scope of the present invention be not limited to it is described
Content, method is conventional method unless otherwise specified in embodiment, and agents useful for same is conventional commercial examination unless otherwise specified
Agent or the reagent prepared according to a conventional method.
Embodiment 1：The preparation method of silver system antibiotic plastic is as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 85 DEG C are put into reactor by 1.5 ratio
In, it is reacted under the conditions of 85 DEG C of temperature, rotating speed 500r/min, silica gel sol system, wherein silicic acid is obtained after reacting 10min
The mass concentration of sodium solution is 5 %, and the mass concentration of sodium bicarbonate solution is 10%；
（2）By volume 1:1.5 ratio measures sodium silicate solution and sodium bicarbonate solution and is preheated to 85 DEG C, then respectively
Reactor rotating speed is adjusted to 100 r/min；Preheated sodium silicate solution and sodium bicarbonate solution are sequentially added into step（1）Silicon
In glue sol system, hi-sil system is obtained after fully reacting 15 min, 0.001mol/L silver nitrate solutions is added, uses nitre
Acid for adjusting pH is made the metal ion of addition be deposited on collosol and gel surface in the form of metal oxide, then reacts 1 h to 5,
Reaction filters at once after stopping, and product need to be washed with deionized 2 times, then is soaked for 3% modifying agent KH550 solution with mass concentration
Rinse is washed 1 time；It puts in 120 DEG C of baking ovens of constant temperature, i.e. acquisition antibacterial silica gel powder body material, wherein sodium silicate solution is taken out after drying 1 h
Mass concentration be 5 %, the mass concentration of sodium bicarbonate solution is 10%；
（3）Polypropylene 80%, antioxidant 1,192 3%, acrylonitrile-butadiene-styrene copolymer are weighed according to percent mass ratio
2%, step（2）Antibacterial silica gel powder 15%；
（4）By step（3）It is in 180 DEG C of mixers that the material weighed, which is put into temperature, and rotor speed is 25 rpm, and the machinery that pressurizes is mixed
1.5 h are closed, are taken out after melting mixing；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, the temperature in each area of double screw extruder
For：One 175 DEG C of area, two 180 DEG C of areas, three 180 DEG C of areas, four 185 DEG C of areas, five 190 DEG C of areas, 195 DEG C of head, extruder rotating speed are 40
Rpm, to which high concentration antibacterial matrices be made；
（6）Mother particles of antibacterial plastics 5%, polypropylene 95% are sufficiently mixed by mass percentage, melts, squeeze out up to antibacterial polypropylene
Plastics；
The anti-microbial property of product is detected using antibacterial experiment.Experimentation is as follows：
First day configuration fluid nutrient medium（5 g of peptone, 2.5 g of saccharomycete, 5 g of sodium chloride, 500 mL of distilled water）, pour into cone
It is shaken up in shape bottle, glass centrifuge tube, fine taper bottle and fluid nutrient medium is put into 40 min of high pressure sterilization in autoclave, it will
Centrifuge tube, fine taper bottle and fluid nutrient medium after sterilizing are put into the double clean bench after ultraviolet sterilization, take 100mL liquid
Body culture medium is put into fine taper bottle for use, is taken 5mL fluid nutrient mediums to be put into centrifuge tube, is waited for fluid nutrient medium temperature in centrifuge tube
When degree is down to room temperature, chooses Escherichia coli with oese and be put into the centrifuge tube equipped with fluid nutrient medium, finally put centrifuge tube
Enter 37 DEG C of constant-temperature table cultures for 24 hours；
It takes within second day the bacterium solution that 1mL is cultivated to be put into for use fine taper bottle, conical flask is put into 37 DEG C of constant-temperature table culture 3h,
Next, configuration solid medium（10 g of peptone, 5 g of saccharomycete, 5 g of sodium chloride, 15 g of agar, 1000 mL of distilled water）,
It pours into conical flask and shakes up, centrifuge tube, spreading rod, pipette, solid medium, the culture dish etc. needed for antibacterial experiment are put into
40 min of high pressure sterilization in autoclave；Solid medium is poured into sterilized culture dish after sterilizing, places asepsis ring
It is cooling for use under border；Cultured Escherichia coli are diluted to a concentration of 5.0 × 105-10×105Cfu/mL bacterial solutions, cutting
（50±2）mm×（50±2）Mm, thickness are not more than the antibiotic plastic sample and blank sample to be detected of 5 mm, clip sanitation-grade
High density polyethylene (HDPE), size are（40±2）mm×（40±2）Mm, thickness are 0.05-0.1 mm.To used antibiotic plastic
70% alcohol solution dipping of sample, blank sample and cover film takes out after 1 min, aseptic water washing is used in combination；It then will be to be checked
The antibiotic plastic and blank sample of survey are respectively placed in sterilized culture dish, and 0.1 ± 0.01 mL is taken to be configured respectively
Bacterium solution is added drop-wise on antibiotic plastic sample and blank sample.Cover film is attached to antibiotic plastic sample and blank sample with tweezers
On, ensure that bacterium solution is uniformly dispersed on antibiotic plastic sample and blank sample.Number is carried out, plane ware is put into 37 DEG C of perseverance
In warm incubator, 24 h are cultivated；
Third day takes out all samples, and antibiotic plastic sample and blank sample are all put into the wide-mouth bottle of gone out bacterium and the number of finishing
In, then 50 mL distilled water are separately added into as eluent into the wide-mouth bottle equipped with sample, wide-mouth bottle is positioned over oscillator
On, eluent after standing, is done gradient dilution to 1.0 × 10 by 20 min of fully shaking3-5×103 Cfu/mL is finally drawn
100 μ l bacterium solutions are inoculated on solid medium, and every group is done three Duplicate Samples, and uniform coated plate.The culture dish for coating plate is put
It is placed in 37 DEG C of constant incubator, culture 18-24 h；Antibiotic rate is calculated using viable bacteria colony counting method；Antibiotic rate result
It see the table below；
。
Embodiment 2：The preparation method of silver-lutetium antibiotic plastic is as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 80 DEG C are put into reactor by 1.3 ratio,
It is reacted at 80 DEG C of temperature, rotating speed 400r/min, silica gel sol system, wherein sodium silicate solution is obtained after reacting 15min
Mass concentration be 10 %, the mass concentration of sodium bicarbonate solution is 5%；
（2）By volume 1:1.3 ratios measure sodium silicate solution and sodium bicarbonate solution and are preheated to 80 DEG C, then will respectively
Reactor rotating speed is adjusted to 150 r/min；Step is added in the preheated above solution in order（1）Silica gel sol system in,
Hi-sil system is obtained after fully reaction 20min, 0.0002mol/L silver nitrate solutions is added, is added after anti-2 min
0.005mol/L lutecium nitrates make the metal ion of addition be deposited on colloidal sol in the form of metal oxide with nitre acid for adjusting pH to 6
Gel surface, then reacts 1.5 h, and reaction filters at once after stopping, and product need to be washed with deionized 2 times, then with a concentration of
5% modifying agent KH560 solution impregnations wash 2 times；It puts in 100 DEG C of baking ovens of constant temperature, is taken out after drying to 1.5 h and obtain antibacterial silica gel
Powder body material, the wherein mass concentration of sodium silicate solution are 10 %, and the mass concentration of sodium bicarbonate solution is 5%；
（3）Polypropylene 84%, antioxidant 1010 3%, haloflex 1%, step are weighed according to percent mass ratio（2）Antimicrobial silicon
Rubber powder body 12%；
（4）By step（3）It is in 190 DEG C of mixers that the material weighed, which is put into temperature, and rotor speed is 30 rpm, and the machinery that pressurizes is mixed
2 h are closed, are taken out after melting mixing；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, the temperature in each area of double screw extruder
For：One 180 DEG C of area, two 180 DEG C of areas, three 185 DEG C of areas, four 185 DEG C of areas, five 190 DEG C of areas, 195 DEG C of head, extruder rotating speed are 50
Rpm, to which high concentration antibacterial matrices be made；
（6）Mother particles of antibacterial plastics 7%, polypropylene 93% are sufficiently mixed by mass percentage, melts, squeeze out up to antibacterial polypropylene
Plastics.
Antibacterial experiment detection is carried out using film applicator coating, step such as embodiment 1 detects the antibacterial effect of silver-lutetium antibiotic plastic,
As a result it see the table below；
。
Embodiment 3：The preparation method of silver-scandium antibiotic plastic is as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 90 DEG C are put into reactor by 1.4 ratio,
It is reacted at 90 DEG C of temperature, rotating speed 400r/min, silica gel sol system, wherein sodium silicate solution is obtained after reacting 20min
Mass concentration be 15 %, the mass concentration of sodium bicarbonate solution is 10%；
（2）By volume 1:1.4 ratios measure sodium silicate solution and sodium bicarbonate solution and are preheated to 90 DEG C, then will respectively
Reactor rotating speed is adjusted to 200 r/min；Step is added in the preheated above solution in order again（1）Silica gel sol system
In, hi-sil system is obtained after fully reacting 25 min, 0.001mol/L silver nitrate solutions is added, is added after anti-3 min
0.01 mol/L scandium nitrates make the metal ion of addition be deposited in the form of metal oxide molten with nitre acid for adjusting pH to 5.5
Glue gel surface, then reacts 2 h, and reaction filters at once after stopping, and product need to be washed with deionized 3 times, then with a concentration of
7% modifying agent KH151 solution impregnations wash 1 time；It puts in 110 DEG C of baking ovens of constant temperature, i.e. acquisition antibacterial silica gel powder is taken out after drying 2 h
Material, the wherein mass concentration of sodium silicate solution are 15 %, and the mass concentration of sodium bicarbonate solution is 10%；
（3）Polyethylene 85%, antioxidant 1076 1.5%, ethylene-vinyl acetate copolymer 1% are weighed according to percent mass ratio,
Step（2）Antibacterial silica gel powder 12.5%；
（4）By step（3）It is in 200 DEG C of mixers that the material weighed, which is put into temperature, and rotor speed is 36 rpm, and the machinery that pressurizes is mixed
2.5 h are closed, are taken out after melting mixing；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, the temperature in each area of double screw extruder
For：One 160 DEG C of area, two 165 DEG C of areas, three 175 DEG C of areas, four 180 DEG C of areas, five 185 DEG C of areas, 195 DEG C of head, extruder rotating speed are 60
Rpm, to which high concentration antibacterial matrices be made；
（6）Mother particles of antibacterial plastics 9%, polyethylene 91% are sufficiently mixed by mass percentage, melts, squeeze out up to antibacterial polyethylene
Plastics.
Antibacterial experiment detection is carried out using film applicator coating, step such as embodiment 1 detects the antibacterial effect of silver-scandium antibiotic plastic,
As a result it see the table below；
。
Embodiment 4：The preparation method of zinc-cerium antibiotic plastic is as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 75 DEG C are put into reactor by 1.5 ratio,
It is reacted at 75 DEG C, rotating speed 500r/min, silica gel sol system, the wherein matter of sodium silicate solution is obtained after reacting 10min
A concentration of 5 % is measured, the mass concentration of sodium bicarbonate solution is 8%；
（2）By volume 1:1.5 ratios measure sodium silicate solution and sodium bicarbonate solution and are preheated to 75 DEG C, then will respectively
Reactor rotating speed is adjusted to 100 r/min；Step is added in the preheated above solution in order again（1）Silica gel sol system
In, hi-sil system is obtained after fully reacting 20 min, 0.8mol/L solution of zinc sulfate is added, is added after anti-5 min
0.01mol/L cerous nitrates make the metal ion of addition be deposited on colloidal sol in the form of metal oxide with nitre acid for adjusting pH to 6
Gel surface, then reacts 1.5 h, and reaction filters at once after stopping, and product need to be washed with deionized 3 times, then with a concentration of
6% modifying agent KH151 solution impregnations wash 1 time；It puts in 120 DEG C of baking ovens of constant temperature, i.e. acquisition antibacterial silica gel powder is taken out after drying 2 h
Material, the wherein mass concentration of sodium silicate solution are 5 %, and the mass concentration of sodium bicarbonate solution is 8%；
（3）Polyethylene 84%, antioxidant 1,192 1.5%, acrylonitrile-butadiene-styrene (ABS) copolymerization are weighed according to percent mass ratio
Object 1.5%, step（2）Antibacterial silica gel powder 13%；
（4）By step（3）It is in 190 DEG C of mixers that the material weighed, which is put into temperature, and rotor speed is 25 rpm, and the machinery that pressurizes is mixed
2.5 h are closed, are taken out after melting mixing；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, the temperature in each area of double screw extruder
For：One 150 DEG C of area, two 165 DEG C of areas, three 170 DEG C of areas, four 175 DEG C of areas, five 180 DEG C of areas, 190 DEG C of head, extruder rotating speed are 55
Rpm, to which high concentration antibacterial matrices be made；
（6）Mother particles of antibacterial plastics 10%, polyethylene 90% are sufficiently mixed by mass percentage, melts, squeeze out up to the poly- second of antibacterial
Alkene plastics.
Antibacterial experiment detection is carried out using film applicator coating, step such as embodiment 1 detects the antibacterial effect of zinc-cerium antibiotic plastic, as a result
It see the table below；
。
Embodiment 5：The preparation method of zinc-holmium antibiotic plastic is as follows：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 70 DEG C are put into reactor by 1.2 ratio,
It is reacted at 70 DEG C, rotating speed 450r/min, silica gel sol system, the wherein matter of sodium silicate solution is obtained after reacting 15min
A concentration of 12 % is measured, the mass concentration of sodium bicarbonate solution is 5%；
（2）By volume 1:1.2 ratios measure sodium silicate solution and sodium bicarbonate solution and are preheated to 70 DEG C, then will respectively
Reactor rotating speed is adjusted to 150 r/min；Step is added in the preheated above solution in order again（1）Silica gel sol system
In, hi-sil system is obtained after fully reacting 20 min, 0.8mol/L solution of zinc sulfate is added, is added after anti-2 min
0.9mol/L holmium nitrates make the metal ion of addition be deposited on colloidal sol in the form of metal oxide solidifying with nitre acid for adjusting pH to 6
2.5h is then reacted on glue surface, and reaction filters at once after stopping, and product need to be washed with deionized 2 times, then be changed with a concentration of 9%
Property agent KH570 solution impregnations wash 1 time；It puts in 100 DEG C of baking ovens of constant temperature, i.e. acquisition antibacterial silica gel powder material is taken out after drying 2.5 h
Material, the wherein mass concentration of sodium silicate solution are 12%, and the mass concentration of sodium bicarbonate solution is 5%；
（3）Polypropylene 82%, antioxidant 1010 2%, haloflex 2%, step are weighed according to percent mass ratio（2）Antimicrobial silicon
Rubber powder body 14%；
（4）By step（3）It is in 200 DEG C of mixers that the material weighed, which is put into temperature, and rotor speed is 36 rpm, and the machinery that pressurizes is mixed
3h is closed, is taken out after melting mixing；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, the temperature in each area of double screw extruder
For：One 175 DEG C of area, two 185 DEG C of areas, three 185 DEG C of areas, four 190 DEG C of areas, five 195 DEG C of areas, 200 DEG C of head, extruder rotating speed are 60
Rpm, to which high concentration antibacterial matrices be made；
（6）Mother particles of antibacterial plastics 8%, polypropylene 92% are sufficiently mixed by mass percentage, melts, squeeze out up to antibacterial polypropylene
Plastics.
Antibacterial experiment detection is carried out using film applicator coating, step such as embodiment 1 detects the antibacterial effect of zinc-holmium antibiotic plastic, as a result
It see the table below；
。
Claims (9)
1. a kind of preparation method of antibiotic plastic, it is characterised in that carry out according to the following steps：
（1）By volume 1:The sodium silicate solution and sodium bicarbonate solution that are preheated to 70-90 DEG C are put by the ratio of 1.1-1.5
It in reactor, is reacted under the conditions of 70-90 DEG C of temperature, rotating speed 300-500r/min, silica gel is obtained after reacting 10-25min
Sol system；
（2）By volume 1:The ratio of 1.1-1.5 measures sodium silicate solution and sodium bicarbonate solution and is preheated to 70-90 respectively
DEG C, reactor rotating speed is then adjusted to 100-200r/min；Preheated sodium silicate solution and sodium bicarbonate solution are added successively
Enter step（1）Silica gel sol system in, obtain hi-sil system after fully reacting 15-30 min, add a concentration of 9 ×
10-5The metal ion solution of -1mol/L is adjusted with acid pH to 5-6, and the metal ion of addition is made to sink in the form of metal oxide
Product is on collosol and gel surface, the reaction was continued 0.5-3h, and reaction filters at once after stopping, and product is washed with deionized 2-3 times, then
It is washed 1-2 times with the modifier solution infiltration of mass concentration 1%-9%, is finally placed at 100-120 DEG C dry 1-3 h, taking-up is
Obtain antibacterial silica gel powder；
（3）Plastic substrate 80%-88%, antioxidant 1%-3%, plasticizer 1%-2%, step are weighed according to mass percent（2）It is anti-
Bacterium silica gel powder 10-15%；
（4）By step（3）Mixture is put into mixer, is taken out after melting mixing, and wherein mixer temperature in use is 170-
In 200 DEG C of mixers, rotor speed is 25-36 rpm；
（5）By step（4）The material of mixing, which is put into double screw extruder, to be granulated, and mother particles of antibacterial plastics is made；
（6）Mother particles of antibacterial plastics 5%-10%, plastic substrate 90%-95% are sufficiently mixed by mass percentage, melts, squeeze out i.e.
Obtain antibiotic plastic.
2. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：The mass concentration of sodium silicate solution is
The mass concentration of 5-15 %, sodium bicarbonate solution are 5-10%.
3. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Metal ion solution be silver nitrate,
One kind in zinc sulfate.
4. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Modifying agent be KH550, KH560,
One kind in KH570, KH151.
5. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Antioxidant is antioxidant 1192, antioxygen
One kind in agent 1010, antioxidant 1076.
6. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Plasticizer is acrylonitrile-butadiene-benzene
One kind in ethylene copolymer, haloflex, ethylene-vinyl acetate copolymer.
7. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Plastic substrate is polypropylene or poly- second
Alkene.
8. the preparation method of antibiotic plastic according to claim 1, it is characterised in that：Step（2）Middle addition metal ion is molten
Liquid reacts the rare earth ion salting liquid of addition concentration 0.001-1mol/L after 2-6min, is adjusted with acid pH to 5-6, the reaction was continued
Gel-like product, the wherein volume ratio 1 of metal ion solution and rare earth ion salting liquid are obtained after 0.5-3 h:1-3:1.
9. the preparation method of antibiotic plastic according to claim 8, it is characterised in that：Rare earth ion salt is lanthanum nitrate, nitric acid
One kind in cerium, lutecium nitrate, yttrium nitrate, scandium nitrate, holmium nitrate.
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| CN109505191A (en) * | 2018-11-15 | 2019-03-22 | 昆明理工大学 | A kind of preparation method of antibacterial environment protection paper |
| CN111621075A (en) * | 2020-06-11 | 2020-09-04 | 合肥市兴烨包装材料有限公司 | Preparation method of pearl cotton particles for pillow inner material |
| CN112679822A (en) * | 2020-12-17 | 2021-04-20 | 厦门翔鹭化纤股份有限公司 | Preparation method and application of antibacterial polyethylene master batch |
| CN112898724A (en) * | 2021-02-23 | 2021-06-04 | 滁州米润科技有限公司 | Long-acting antibacterial ABS plastic and preparation method and application thereof |
| CN113292688A (en) * | 2021-04-08 | 2021-08-24 | 珠海中车装备工程有限公司 | Preparation method of composite antibacterial agent and antibacterial plastic |
| CN115260411A (en) * | 2022-09-20 | 2022-11-01 | 南通为华创新材料科技有限公司 | Medical composite material and preparation method thereof |
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