CN105623132A - Antibiotic polystyrene material and preparation method thereof - Google Patents
Antibiotic polystyrene material and preparation method thereof Download PDFInfo
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- CN105623132A CN105623132A CN201410588986.9A CN201410588986A CN105623132A CN 105623132 A CN105623132 A CN 105623132A CN 201410588986 A CN201410588986 A CN 201410588986A CN 105623132 A CN105623132 A CN 105623132A
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- agent
- antibacterial
- styrene
- butadiene rubber
- antibacterial agent
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 73
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000003115 biocidal effect Effects 0.000 title abstract 6
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 99
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000000844 anti-bacterial effect Effects 0.000 claims description 64
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 229920001971 elastomer Polymers 0.000 claims description 34
- 239000005060 rubber Substances 0.000 claims description 34
- 239000004599 antimicrobial Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 14
- 229920002857 polybutadiene Polymers 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 13
- -1 silver ions Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000003712 anti-aging effect Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical group CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
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- 239000002904 solvent Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000004283 biguanides Chemical class 0.000 claims description 3
- 229940073505 ethyl vanillin Drugs 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 2
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229940123208 Biguanide Drugs 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003577 thiophenes Chemical class 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims 1
- 239000006057 Non-nutritive feed additive Substances 0.000 claims 1
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002421 anti-septic effect Effects 0.000 abstract 3
- 239000000843 powder Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229920002413 Polyhexanide Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
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- 229920003023 plastic Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NZWXMOTXTNDNLK-UHFFFAOYSA-N [Cu].[Zn].[Ag] Chemical compound [Cu].[Zn].[Ag] NZWXMOTXTNDNLK-UHFFFAOYSA-N 0.000 description 1
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- 239000004566 building material Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides an antibiotic polystyrene material and a preparation method thereof. The antiseptic uniformly-dispersed polystyrene polymer material is prepared through adding an antiseptic to a polymerization system in a form of a supported antiseptic with styrene butadiene rubber as a carrier. The antibiotic polystyrene material has good antibiosis effect and antibiosis endurance, and also has good mechanical performances and processing performance, such as high impact resistance. Additionally, the preparation method of the antibiotic polystyrene material has the advantages of simple process and realization of online production in an industrial apparatus.
Description
Technical Field
The invention relates to the technical field of polystyrene materials and preparation thereof, in particular to an antibacterial polystyrene material and a preparation method thereof.
Background
Polystyrene (PS) has been widely used in various industrial and civil fields because of its characteristics of hard quality, good transparency, rigidity, electrical insulation, low hygroscopicity, low price, easy dyeing, easy processing, no temperature variation of thermal conductivity coefficient, etc., and has become one of the four common plastics. Due to the influence of environmental pollution and other reasons, in the fields of medical materials, household appliances, building materials and the like in which polystyrene is applied, materials are often required to have certain antibacterial property, so that the safety and health of users are ensured. Therefore, the development and research of the polystyrene product with antibacterial property have very important practical significance for improving the living environment of people, reducing the incidence of diseases and protecting the health of human bodies.
The types of antibacterial agents mainly include inorganic antibacterial agents, organic antibacterial agents, complex antibacterial agents and the like, and various patents have been issued for the development and research of antibacterial agents. Inorganic antimicrobial agents are the most commonly used antimicrobial agents and mainly contain metals such as silver, copper, zinc, etc. in the form of ions, which are bound to a carrier by ion exchange or other means. The antibacterial mechanism of inorganic antibacterial agents is that these metal ions can strongly bind to the active enzyme centers of bacteria or molds, thereby disrupting the growth and reproduction of bacteria or molds. US6641842, US6582715 disclose inorganic antibacterial agent loaded with metal ions such as gold, silver, copper, zinc, etc., and chinese patents CN101125458, CN101142919 disclose inorganic antibacterial agent loaded with silver ions and zinc-silver-copper complex ions, respectively. The organic antibacterial agent mainly comprises vanillin, ethyl vanillin compounds, quaternary ammonium salts, biguanide compounds, alcohols, phenols, organic metals, pyridine compounds and the like. The antibacterial mechanism of organic antibacterial agents is generally considered to be that they bind to anions on the cell membrane surface of bacteria and molds or react with sulfydryl groups to destroy the synthetic system of proteins and cell membranes and inhibit the propagation of bacteria and molds. The composite antibacterial agent is used for solving the weak point of the antibacterial performance of a certain single antibacterial agent, combining the advantages of other antibacterial agents in the aspect of antibacterial performance, combining the two antibacterial agents to enable the antibacterial agent to have a specific or stronger antibacterial function, and prolonging the antibacterial time of the material.
Currently, plastic products having antibacterial properties are mainly obtained by directly mixing an antibacterial agent with plastic. For example, the antibacterial polystyrene composition provided by patent CN102276937A is prepared by uniformly mixing polystyrene, composite antibacterial agent, etc., and melt blending. Although the method has simple process, the dispersibility of the antibacterial agent in the plastic is poor, and the antibacterial agent particles are easy to agglomerate, so that the antibacterial effect is poor, the antibacterial agent is not fully utilized, and the use cost is increased.
The preparation method of the antibacterial polystyrene provided by patent CN103205080A is to form a nano titanium dioxide film layer on the surface of the polystyrene material by a plasma sputtering process after the polystyrene material is molded. Although the antibacterial polystyrene prepared by the method can greatly save the using amount of the antibacterial agent, the antibacterial polystyrene has a defect in the aspect of antibacterial durability.
Disclosure of Invention
In view of the above-mentioned drawbacks in the prior art, the present invention provides a polystyrene material with antibacterial properties, wherein the antibacterial agent has good dispersibility in the material, and the material has good antibacterial effect and antibacterial durability, and simultaneously has high impact resistance.
The invention also provides a method for preparing the antibacterial polystyrene material.
According to the invention, an antibacterial polystyrene material is provided, which comprises polystyrene, toughened rubber, styrene-butadiene rubber and an antibacterial agent, wherein the antibacterial agent is dispersed in a matrix of the polystyrene, the toughened rubber and the styrene-butadiene rubber. Wherein styrene-butadiene rubber is added to the antibacterial polystyrene material in the form of a carrier as an antibacterial agent. The styrene butadiene rubber is used as a carrier of the antibacterial agent, so that the antibacterial agent can be more uniformly dispersed in a raw material system for preparing the polystyrene, and the dissolubility of the antibacterial agent in the raw material system for preparing the polystyrene can be improved through the mediation effect of the styrene butadiene rubber, and the styrene butadiene rubber and the toughening rubber can play a role in synergistic toughening. In addition, the "dispersion" means that the antibacterial agent is uniformly dispersed in the polystyrene material system, and more specifically, such "dispersion" is understood to mean that the antibacterial agent is microscopically uniformly dispersed in the polystyrene material system; thus, the "dispersion" cannot be achieved by simply mechanically mixing the antimicrobial agent with a material formed of a matrix of polystyrene, toughened rubber and styrene butadiene rubber.
The toughening rubber may be selected from those commonly used in the art, such as butadiene rubber. The addition of the toughening rubber can increase the impact resistance of the polystyrene material.
The antibacterial agent (i.e., the antibacterial active ingredient) used in the present invention may be an inorganic metal ion antibacterial agent, an organic antibacterial agent, or a composite antibacterial agent composed of an inorganic metal ion antibacterial agent and an organic antibacterial agent. Wherein the inorganic metal ion antibacterial agent may be at least one selected from silver ion, zinc ion, copper ion and calcium ion. The organic antibacterial agent may be at least one selected from quaternary ammonium salts, biguanides, alcohols, phenols, vanillin, ethylvanillin, pyridines, imidazoles, thiophenes, and organic metals. In the present invention, silver ion is preferable as the antibacterial agent.
In the polystyrene material provided by the invention, the weight content of the antibacterial agent is 200ppm to 10000ppm, preferably 500ppm to 5000ppm, more preferably 800ppm to 3000ppm, and most preferably 1000ppm to 2000 ppm. If the content of the antibacterial agent is too low, no significant antibacterial effect is obtained, and if the content is too high, the cost of the product is increased.
In order to further enhance other properties of the antibacterial polystyrene material, the antibacterial polystyrene material provided by the invention can further comprise other auxiliary agents, such as at least one of an anti-aging agent, a heat stabilizer and a processing auxiliary agent. Wherein the anti-aging agent may be at least one selected from the group consisting of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate (1010), tris (2, 4-di-tert-butyl) phenyl phosphite (168), dioctadecyl pentaerythrityl diphosphite (618), N-cyclohexyl-N '-phenyl-p-phenylenediamine (4010), 2' -methylenebis (4-methyl-6-tert-butyl) phenol (2246), and octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate (1076); the heat stabilizer may be at least one selected from zinc stearate, lead stearate and cadmium stearate.
Preferably, in the antibacterial polystyrene material, the viscosity-average molecular weight of polystyrene is in the range of 5 to 10 ten thousand (the weight-average molecular weight is between 10 and 40 ten thousand). For polystyrene polymers, a viscosity average molecular weight of less than 5 ten thousand results in very low mechanical strength, a molecular weight of more than 10 ten thousand, and poor processability. Therefore, the antibacterial polystyrene provided by the invention has the viscosity average molecular weight within the range of 5-10 ten thousand, and not only has good mechanical properties, but also has good processability.
In one embodiment, the polystyrene has a viscosity average molecular weight in the range of 5 to 10 ten thousand; and/or the total weight content of the styrene-butadiene rubber and the toughened rubber is 3-15 percent; the toughening rubber is preferably butadiene rubber.
In a preferred embodiment, the material is obtained by adding a supported antibacterial agent with styrene-butadiene rubber as a carrier to a mixture comprising styrene monomer and toughening rubber and initiating polymerization. It is stated herein that the term "supported antimicrobial agent" and "antimicrobial agent" alone are used herein to be understood in a differentiated manner, with "antimicrobial agent" referring to the unsupported antimicrobial agent and "supported antimicrobial agent" being an overall concept comprising both the "antimicrobial agent" (i.e., the antimicrobial active ingredient) and the carrier supporting the "antimicrobial agent". In short, an "antimicrobial agent" is a single antimicrobial active ingredient, while a "supported antimicrobial agent" includes both an antimicrobial active ingredient and a carrier. As mentioned above, the antibacterial agent is added in the form of a supported antibacterial agent taking styrene butadiene rubber as a carrier, so that the styrene butadiene rubber not only helps the antibacterial agent to be better dissolved in a polymerization system and more uniformly dispersed in a polymer product, but also the styrene butadiene rubber as the carrier can synergistically play a toughening role with the toughening rubber. Meanwhile, in order to achieve a better toughening effect, the total weight content of the styrene-butadiene rubber and the toughening rubber in the antibacterial polystyrene material is 3-15%.
Wherein the supported antibacterial agent can be prepared by the following method: adding an antibacterial agent (in a certain proportion) into styrene butadiene rubber emulsion, adding a cross-linking agent, carrying out cross-linking reaction under the irradiation of high-energy rays, and drying a cross-linking reaction product to obtain a supported antibacterial agent taking styrene butadiene rubber as a carrier; wherein the crosslinking agent may be selected from at least one of octyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol methacrylate, divinylbenzene, trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate; high-energy source ray irradiation can be carried out by adopting a cobalt source, X-rays, ultraviolet rays or a high-energy electron accelerator, the cobalt source is preferably selected for irradiation, the dose is 2.5Mrad, and the dose rate is 50 Gy/min; drying can be carried out by spray drying or precipitation drying, preferably by spray drying, at an inlet temperature of, for example, 100 ℃ to 200 ℃ and an outlet temperature of, for example, 20 ℃ to 80 ℃. Collecting the dried nano-scale antibacterial rubber particles with certain gel content in a cyclone separator.
Preferably, the gel content of the load-type antibacterial agent is more than or equal to 60 wt%; and/or a swelling index of less than or equal to 15; and/or a particle size of 100-1000 nm. In the present invention, the selection of such a supported antibacterial agent not only allows the antibacterial action to be sufficiently exerted, but also does not adversely affect the mechanical properties of the polystyrene material itself.
The invention also provides a preparation method of the antibacterial polystyrene material, which comprises the steps of adding the supported antibacterial agent taking styrene-butadiene rubber as a carrier and the toughening rubber into a styrene monomer, uniformly mixing, optionally adding an organic solvent, then initiating free radical polymerization by thermal initiation or an initiator, optionally removing residual monomer and solvent to obtain the antibacterial polystyrene material, wherein an auxiliary agent is optionally added before or after the polymerization. Also, it is preferable to add an auxiliary before the polymerization. The process comprises the dissolution of the supported antibacterial agent and the toughening rubber, the grafting of styrene monomer on the toughening rubber and the polymerization of styrene. The dispersibility of the antibacterial agent in the polystyrene material prepared by the method is obviously higher than that of a product prepared by mechanically blending the polystyrene polymer and the antibacterial agent in the prior art, so that the polystyrene material has better antibacterial performance.
In a preferred embodiment, the free radical polymerization is carried out in three stages: reacting at 100-130 deg.C for 4 hr, at 130-140 deg.C for 2 hr, and at 140-170 deg.C for 1.5 hr. Considering that the molecular weight of polystyrene has a great influence on the properties thereof, and the inventors of the present invention found in the course of experiments that the polymerization temperature is a major factor affecting the molecular weight of the polymer, the higher the reaction temperature, the more active centers are formed, the faster the reaction rate, the lower the molecular weight of the polymer, and the lower the reaction temperature rises by 10 ℃ to 20 ℃, and the molecular weight decreases by several times. Therefore, the invention controls the polymerization temperature to be 100-170 ℃ and the pressure to be normal pressure. Further, in order to control the molecular weight of the polymer and increase the monomer conversion, the present invention takes the form of a stepwise polymerization, i.e., selecting the polymerization times corresponding to the polymerization temperatures at different polymerization temperatures, and specifically, conducting the polymerization by the three-stage process as described above. The result is an antibacterial polystyrene material with a viscosity average molecular weight in the range of 5-10 ten thousand, which not only has good mechanical properties and processability, but also obtains a higher conversion rate of styrene monomer.
In the method as described above, the toughening rubber may be a butadiene rubber; the organic solvent is preferably selected from aromatic hydrocarbons, such as toluene, xylene or ethylbenzene, etc.; the initiator may be selected from at least one of potassium persulfate, dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide and di-tert-butyl peroxide, and is preferably cumene hydroperoxide; the auxiliary agent is, for example, an anti-aging agent or a heat stabilizer, wherein the anti-aging agent and the heat stabilizer may be selected from at least one of the substances described above.
Preferably, the loading-type antibacterial agent is added in an amount of 500ppm to 8000ppm, preferably 800ppm to 2000ppm based on the weight of the antibacterial agent in the loading-type antibacterial agent based on the weight of the styrene; the addition amount of the toughening rubber is 5-10% by weight based on the addition amount of the styrene, and is preferably 6-8%; the addition amount of the initiator is 0.1-2% by weight based on the addition amount of the styrene; the amount of the organic solvent added is 0 to 60% by weight, preferably 10 to 30% by weight based on the amount of styrene added.
In a preferred embodiment, after the supported antibacterial agent and the toughened rubber are added into the styrene monomer, stirring and dissolving are carried out for 6-10h under the condition of high-speed stirring, so that the supported antibacterial agent and the toughened rubber are fully swelled in the styrene monomer, and then thermal initiation is carried out or a proper amount of initiator is added to initiate polymerization.
The stirring form adopted by the invention can adopt an anchor stirrer, a frame stirrer, a single-spiral-ribbon stirrer, a double-spiral-ribbon stirrer and a bottom triangular plate middle-upper spiral-ribbon stirrer, wherein the spiral ribbon can be a single spiral ribbon or a double spiral ribbon. The invention preferably adopts a screw belt composite stirrer at the middle upper part of a triangular plate at the bottom, and the stirring speed is 100-180 rpm/min, preferably 120-140 rpm/min.
According to the antibacterial polystyrene material provided by the invention, the nano styrene-butadiene rubber powder is used as the carrier of the antibacterial agent, so that the antibacterial agent is uniformly dispersed in the polystyrene material, and therefore, the antibacterial polystyrene material has good antibacterial performance, good antibacterial effect and antibacterial durability. Meanwhile, the styrene butadiene rubber added as a carrier and the toughening rubber play a role in synergistically toughening the polystyrene material together, so that the material has better impact resistance.
The method for producing the antibacterial high impact polystyrene material provided by the invention adds the antibacterial agent into a polymerization system in the form of a supported antibacterial agent taking styrene butadiene rubber as a carrier, thereby obtaining the polystyrene polymer material with the uniformly dispersed antibacterial agent. In addition, the method has simple polymerization process, can realize online production on an industrial device, reduces the loss of mechanical properties of the product caused by high-temperature blending of the double screws in the later processing, not only keeps the advantages of excellent mechanical properties of the impact polystyrene and the like, but also has good antibacterial capability.
Detailed Description
The invention is further described below by way of examples to enhance the understanding of the invention. The following examples are given to better illustrate the invention without limiting it.
The physical property test method comprises the following steps:
(1) notched Izod impact Strength (kJ/m)2): testing according to GB/T1843-2008;
(2) tensile yield stress (MPa): testing according to GB/T1040.2-2006;
(3) and (3) testing antibacterial performance: the JISZ2801 standard test was used. The standard expresses the antibacterial property of the material by an antibacterial activity value R, the antibacterial activity value is more than 2, the antibacterial test of the strain is passed, namely the antibacterial efficiency is more than 99 percent, and the antibacterial rate is 99 percent when the antibacterial activity value is 2.
Example 1
1) Preparation of supported antibacterial agent
Putting commercial carboxylated styrene-butadiene latex (XSBRL-54B 1, product of Yanshan petrochemical industry) with the solid content of 50 wt% into a container, dropwise adding 75g of isooctyl acrylate under stirring, after the dropwise adding is finished, adding 78.7g of silver nitrate, continuously stirring for one hour to completely dissolve the silver nitrate, and then irradiating by using a cobalt source, wherein the dose is 2.5Mrad, and the dose rate is 50 Gy/min. The irradiated latex is spray-dried by a spray dryer, the inlet temperature of the spray dryer is 140-160 ℃, and the outlet temperature is 40-60 ℃. Collecting the dried carboxylated styrene-butadiene rubber powder in a cyclone separator to obtain the free-flowing fully-vulcanized carboxylated styrene-butadiene rubber powder in which silver ions are uniformly dispersed, namely the supported antibacterial agent. The obtained rubber powder was 500g, in which the antibacterial agent silver ion content was 10% by weight, and it was found that the rubber powder had a particle diameter of about 150nm, a gel content of 92.6% and a swelling index of 7.6.
2) Preparation of antibacterial polystyrene material
Adding 15g of the supported antibacterial agent (namely styrene butadiene rubber powder with uniformly dispersed silver ions) obtained in the step 1), 120g of butadiene rubber (A55AE, produced by Shanghai Gaoqiao petrochemical industry), 1700g of styrene (produced by Yanshan petrochemical industry) and 300g of ethylbenzene into a polymerization kettle, uniformly stirring, swelling for 8 hours, and adding 10761.6g of anti-aging agent.
The atmosphere in the polymerization vessel was replaced with nitrogen. The polymerization is carried out by adopting a free radical bulk polymerization method, and the initiation method adopts thermal initiation. The polymerization vessel was heated at a stirring rate of 170rpm, polymerized at 120 ℃ for 4 hours, polymerized at 130 ℃ for 2 hours, and then polymerized at 160 ℃ for 1.5 hours. During the polymerization process, the stirring speed is properly reduced to 100rpm due to the excessive viscosity of the system. After the polymerization process is finished, discharging the viscous body obtained by polymerization, allowing the viscous body to fall into a devolatilizer at 210 ℃, and quickly flashing under a vacuum state to remove unreacted monomers and solvent ethylbenzene. Obtaining 1580g of polymer after devolatilization, wherein the conversion rate of styrene is 85 percent, the total weight percentage content of styrene butadiene rubber and butadiene rubber is 8.5 percent, obtaining a sample through cooling, granulation and sample preparation, and measuring the physical properties of the obtained sample. The results are shown in Table 1.
Comparative example 1
A polystyrene material was prepared by referring to the process conditions and test procedures of step 2) of example 1 except that the supported antibacterial agent using styrene-butadiene rubber powder as a carrier was not added and the amount of butadiene rubber added was changed to 135g so that the total amount of the rubber added was equivalent to that of example 1, and finally a polymer having impact resistance was obtained, the property indexes of which are shown in Table 1.
Comparative example 2
A polystyrene polymer having impact resistance was synthesized according to the method of comparative example 1, and then the polymer and the supported antibacterial agent using styrene-butadiene rubber powder as a carrier, which was prepared through step 1) of example 1, were put into a high-speed mixer and stirred uniformly. Wherein, 99 parts of polystyrene polymer and 1 part of load type antibacterial agent taking styrene butadiene rubber powder as a carrier. The mixed materials were then melt blended by means of a twin-screw extruder (Nanjing Kogya, PE-34). The extrusion temperature is 180-210 ℃, the rotation speed of the screw is 320rpm, and the mixed materials are extruded, granulated and prepared into samples after being blended by double screws. The performance index of the samples is shown in Table 1 below.
Example 2
Referring to the process conditions and test procedures of step 2) of example 1, a polystyrene material was prepared by charging 2.3g of silver nitrate, 135g of butadiene rubber A55AE, 1700g of styrene, 300g of ethylbenzene into a reaction vessel, stirring at 170rpm for 8 hours, and then adding 10761.6g of an antioxidant.
The atmosphere in the polymerization vessel was replaced with nitrogen. The polymerization is carried out by adopting a free radical bulk polymerization method, and the initiation method adopts thermal initiation. The polymerization vessel was heated at a stirring rate of 170rpm, polymerized at 120 ℃ for 4 hours, polymerized at 130 ℃ for 2 hours, and then polymerized at 160 ℃ for 1.5 hours. During the polymerization process, the stirring speed is properly reduced to 100rpm due to the excessive viscosity of the system. After the polymerization process is finished, discharging the viscous body obtained by polymerization, allowing the viscous body to fall into a devolatilizer at 210 ℃, and quickly flashing under a vacuum state to remove unreacted monomers and solvent ethylbenzene. Obtaining 1560g of polymer after devolatilization, wherein the conversion rate of styrene is 83.6 percent, the total weight percentage content of butadiene rubber is 8.65 percent, obtaining a sample through cooling, granulation and sample preparation, and measuring the physical properties of the obtained sample. The results are shown in Table 1.
Example 3
1) Preparation of supported antibacterial agent
A commercially available carboxylated styrene-butadiene latex (XSBRL-54B 1, trade name, available from Yanshan petrochemical company) with a solid content of 50 wt% was placed in a container, 75g of isooctyl acrylate was added dropwise with stirring, after the addition was completed, 50g of polyhexamethylene biguanide hydrochloride (PHMB, manufactured by Utility Co., Ltd., Shanghai) was added, stirring was continued for one hour to completely dissolve PHMB, and then irradiation was performed with a cobalt source at a dose of 2.5Mrad at a dose rate of 50 Gy/min. The irradiated latex is spray-dried by a spray dryer, the inlet temperature of the spray dryer is 140-160 ℃, and the outlet temperature is 40-60 ℃. Collecting the dried carboxylated styrene-butadiene rubber powder in a cyclone separator to obtain the free-flowing fully-vulcanized carboxylated styrene-butadiene rubber powder in which silver ions are uniformly dispersed, namely the supported antibacterial agent. 500g of the obtained rubber powder, in which the content of the antibacterial agent PHMB was 10% by weight, was found to have a particle diameter of about 180nm, a gel content of 92.2% and a swelling index of 7.5.
2) Preparation of antibacterial polystyrene material
30g of the supported organic antibacterial agent (namely styrene butadiene rubber powder with PHMB uniformly dispersed) obtained in the step 1), 105g of butadiene rubber (A55AE, produced by Shanghai Gaoqiao petrochemical industry), 1700g of styrene (produced by Yanshan petrochemical industry) and 300g of ethylbenzene are added into a polymerization kettle, stirred uniformly, swelled for 8 hours, and then added with 10761.6g of anti-aging agent.
The atmosphere in the polymerization vessel was replaced with nitrogen. The polymerization is carried out by adopting a free radical bulk polymerization method, and the initiation method adopts thermal initiation. The polymerization vessel was heated at a stirring rate of 170rpm, polymerized at 120 ℃ for 4 hours, polymerized at 130 ℃ for 2 hours, and then polymerized at 160 ℃ for 1.5 hours. During the polymerization process, the stirring speed is properly reduced to 100rpm due to the excessive viscosity of the system. After the polymerization process is finished, discharging the viscous body obtained by polymerization, allowing the viscous body to fall into a devolatilizer at 210 ℃, and quickly flashing under a vacuum state to remove unreacted monomers and solvent ethylbenzene. Obtaining 1520g of polymer after devolatilization, wherein the conversion rate of styrene is 81.4 percent, the total weight percentage content of styrene butadiene rubber and butadiene rubber is 8.9 percent, obtaining a sample through cooling, granulation and sample preparation, and measuring the physical properties of the obtained sample. The results are shown in Table 1.
Comparative example 3
A polystyrene material was prepared by referring to the process conditions and test procedures of step 2) of example 2, except that 5g of a supported organic antibacterial agent supported on styrene-butadiene rubber powder was added and 105g of butadiene rubber was added without change, to finally obtain a polymer having impact resistance, the property indexes of which are shown in Table 1.
TABLE 1 results of performance test of examples and comparative examples
And (4) conclusion: as shown in the results of example 1, it can be seen from table 1 that the nano-sized styrene-butadiene rubber powder is used as the carrier of the antibacterial agent, and the supported antibacterial agent is added into the styrene monomer polymerization system, so that the antibacterial agent can be uniformly dispersed in the polystyrene material, and the polystyrene material has good antibacterial performance; meanwhile, the styrene butadiene rubber added as a carrier and the toughening rubber play a role in synergistically toughening the polystyrene material together, so that the material has excellent impact resistance.
Compared with the example 1, the antibacterial agent is not added in the comparative example 1, so that the antibacterial effect is avoided, and the styrene butadiene rubber powder used as the carrier of the supported antibacterial agent is added in the example 1, so that the styrene butadiene rubber powder and the butadiene rubber have a synergistic toughening effect, so that the impact resistance of the example 1 is obviously better than that of the comparative example 1; in comparative example 2, although the supported antibacterial agent was used, the antibacterial agent in the antibacterial polystyrene material obtained by mixing it with the polystyrene material by means of mechanical stirring was not uniformly dispersed, and thus the antibacterial effect was not as good as that of example 1; the antibacterial agent used in example 2 is a non-supported antibacterial agent, but a separate antibacterial agent is added before polymerization of styrene monomer, and the antibacterial effect is not as good as that of example 1; in the embodiment 3, a load type organic antibacterial agent taking styrene butadiene rubber as a carrier is used, and the obtained antibacterial polystyrene material has the antibacterial effect and the mechanical property similar to those of the embodiment 1; as can be seen from comparative example 3, if the amount of the added antibacterial agent is too small, the antibacterial effect is very small, the total amount of the added toughening rubber is insufficient, and the impact resistance of the obtained polystyrene material is slightly poor.
Claims (13)
1. An antibacterial polystyrene material, the material comprising polystyrene, toughened rubber, styrene butadiene rubber and an antibacterial agent, wherein the antibacterial agent is dispersed in a matrix of the polystyrene, the toughened rubber and the styrene butadiene rubber.
2. The material of claim 1, wherein the antimicrobial agent is an inorganic metal ion antimicrobial agent, an organic antimicrobial agent, or a composite antimicrobial agent consisting of an inorganic metal ion antimicrobial agent and an organic antimicrobial agent.
3. The material of claim 2, wherein the inorganic metal ion antimicrobial agent is selected from at least one of silver ions, zinc ions, copper ions, and calcium ions; the organic antibacterial agent is at least one selected from quaternary ammonium salts, biguanides, alcohols, phenols, vanillin, ethyl vanillin, pyridines, imidazoles, thiophenes and organic metals.
4. The material according to claim 1, characterized in that the content by weight of the antimicrobial agent is between 500ppm and 5000ppm, preferably between 1000ppm and 2000 ppm.
5. The material of claim 1, further comprising at least one of an anti-aging agent, a thermal stabilizer, and a processing aid.
6. The material according to claim 1, wherein the polystyrene has a viscosity average molecular weight in the range of 5 to 10 ten thousand; and/or the total weight content of the styrene-butadiene rubber and the toughened rubber is 3-15 percent; the toughening rubber is preferably butadiene rubber.
7. The material according to any one of claims 1 to 6, wherein the material is obtained after adding a supported antibacterial agent with styrene-butadiene rubber as a carrier to a mixture comprising styrene monomer and toughening rubber and initiating polymerization.
8. The material of claim 7, wherein the supported antimicrobial agent is prepared by: adding an antibacterial agent into styrene butadiene rubber emulsion, adding a cross-linking agent, carrying out cross-linking reaction under the irradiation of high-energy rays, and drying a cross-linking reaction product to obtain a supported antibacterial agent taking styrene butadiene rubber as a carrier;
wherein,
the cross-linking agent is selected from at least one of octyl methacrylate, isooctyl methacrylate, glycidyl methacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, diethylene glycol methacrylate, divinylbenzene, trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate;
irradiating high-energy source rays by adopting a cobalt source, X-rays, ultraviolet rays or a high-energy electron accelerator;
drying by spray drying or precipitation drying.
9. The material of claim 7, wherein the gel content of the supported antimicrobial agent is greater than or equal to 60 wt%; and/or a swelling index of less than or equal to 15; and/or a particle size of 100-1000 nm.
10. A method for preparing the antibacterial polystyrene material as claimed in any one of claims 1 to 9, said method comprising adding a supported antibacterial agent using styrene-butadiene rubber as a carrier and toughening rubber into styrene monomer, mixing uniformly, and optionally adding an organic solvent, then initiating radical polymerization by thermal initiation or an initiator, optionally removing residual monomer and solvent to obtain the antibacterial polystyrene material; wherein optionally an auxiliary agent is also added before or after the polymerization.
11. The method according to claim 10, wherein the free radical polymerization is carried out in three stages: reacting at 100-130 deg.C for 4 hr, at 130-140 deg.C for 2 hr, and at 140-170 deg.C for 1.5 hr.
12. The method according to claim 10 or 11,
the toughened rubber is butadiene rubber;
the organic solvent is selected from aromatic hydrocarbons;
the initiator is selected from at least one of potassium persulfate, dicumyl peroxide, cumene hydroperoxide, benzoyl peroxide and di-tert-butyl peroxide;
the auxiliary agent is selected from an anti-aging agent or a heat stabilizer, wherein the anti-aging agent is selected from at least one of 2, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, tetra [3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butyl) phenyl phosphite ester, dioctadecyl pentaerythritol diphosphite ester, N-cyclohexyl-N '-phenyl-p-phenylenediamine, 2' -methylene bis (4-methyl-6-tert-butyl) phenol and octadecyl 3, 5-di-tert-butyl-4-hydroxy phenyl propionate; the heat stabilizer is at least one of zinc stearate, lead stearate and cadmium stearate.
13. The method of claim 12,
the addition amount of the load type antibacterial agent is 500ppm to 8000ppm, preferably 800ppm to 2000ppm based on the weight of the antibacterial agent in the load type antibacterial agent based on the addition amount of the styrene;
the addition amount of the toughening rubber is 5-10% by weight based on the addition amount of the styrene, and is preferably 6-8%;
the addition amount of the initiator is 0.1-2% by weight based on the addition amount of the styrene;
the amount of the organic solvent added is 0 to 60% by weight, preferably 10 to 30% by weight based on the amount of styrene added.
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| CN115669683A (en) * | 2022-11-04 | 2023-02-03 | 国科温州研究院(温州生物材料与工程研究所) | Preparation method and application of novel copper-zinc-doped carbonic acid-based antibacterial film aid |
| CN115669683B (en) * | 2022-11-04 | 2024-07-12 | 国科温州研究院(温州生物材料与工程研究所) | Preparation method and application of novel copper-zinc doped carbonic acid-based antibacterial film auxiliary agent |
| CN116715794A (en) * | 2023-04-19 | 2023-09-08 | 天津仁泰新材料股份有限公司 | Plastic substrate master batch production process and substrate master batch |
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