CN105238057A - Preparation method of antibiosis silicone rubber - Google Patents
Preparation method of antibiosis silicone rubber Download PDFInfo
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- CN105238057A CN105238057A CN201510645206.4A CN201510645206A CN105238057A CN 105238057 A CN105238057 A CN 105238057A CN 201510645206 A CN201510645206 A CN 201510645206A CN 105238057 A CN105238057 A CN 105238057A
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- silicon rubber
- solution
- water glass
- germicide
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 211
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 16
- 230000003115 biocidal effect Effects 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims description 168
- 238000003756 stirring Methods 0.000 claims description 95
- 235000019353 potassium silicate Nutrition 0.000 claims description 91
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 91
- 230000000845 anti-microbial effect Effects 0.000 claims description 62
- 239000006185 dispersion Substances 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 54
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 48
- 239000011259 mixed solution Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 33
- -1 polydimethylsiloxane Polymers 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 238000002203 pretreatment Methods 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 230000001186 cumulative effect Effects 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 238000007493 shaping process Methods 0.000 claims description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 11
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 11
- 229960001763 zinc sulfate Drugs 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical group [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000002253 acid Substances 0.000 claims description 3
- 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 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [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
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000011550 stock solution Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract description 2
- 206010059866 Drug resistance Diseases 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 62
- 230000000844 anti-bacterial effect Effects 0.000 description 31
- 241000894006 Bacteria Species 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000000523 sample Substances 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229920000260 silastic Polymers 0.000 description 6
- 241000607142 Salmonella Species 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
- 230000000968 intestinal effect Effects 0.000 description 4
- 239000006101 laboratory sample Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RFYTWKQWFTUQKQ-UHFFFAOYSA-N [Zn].[Gd] Chemical class [Zn].[Gd] RFYTWKQWFTUQKQ-UHFFFAOYSA-N 0.000 description 3
- 238000005267 amalgamation Methods 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- FQVNUZAZHHOJOH-UHFFFAOYSA-N copper lanthanum Chemical class [Cu].[La] FQVNUZAZHHOJOH-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000036039 immunity Effects 0.000 description 3
- 239000002362 mulch Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 206010016952 Food poisoning Diseases 0.000 description 2
- 208000019331 Foodborne disease Diseases 0.000 description 2
- NRYDISAKNPQQOL-UHFFFAOYSA-N [Ag].[Ho] Chemical compound [Ag].[Ho] NRYDISAKNPQQOL-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010039438 Salmonella Infections Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002183 duodenal effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 230000002550 fecal effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 230000004054 inflammatory process Effects 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920002529 medical grade silicone Polymers 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 206010039447 salmonellosis Diseases 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 description 1
- 229940033663 thimerosal Drugs 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a preparation method of antibiosis silicone rubber. The method comprises the following steps: adhering antibiosis ions to a white carbon black carrier through a sol-gel technology to obtain antibiosis gel, adding a preprocessed silicone rubber stock solution, and fully fusing and curing to prepare a silicone rubber material with antibiosis ability. The antibiosis silicone rubber prepared through the method has the advantages of high sterilization rate, excellent mechanical performances, no generation of drug resistance,, strong antibiosis broad spectrum activity, safety to human bodies and environment, simple preparation process conditions, low cost and considerable application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of antimicrobial silicon rubber.
Background technology
Silicone rubber products is widely used in the fields such as medical treatment, life, industry.As medical catheter, prosthesis, obturator, artificial tracheae, artificial lung, artificial bone, silicon rubber duodenal tube etc., also for phone housing, children's nipple etc.But due to the structure that it is special, surface easily particle-bound bacteria and fungi thus cause disease to the mankind.Anti-biotic material, as a kind of new function material, effectively can suppress the microorganism that the bacterium in surrounding environment, germ etc. are harmful.Therefore, antibacterial effect is remarkable, of many uses, eco-friendly inorganic antibacterial is combined with silicon rubber and obtains antimicrobial silicon elastomeric material and become the emphasis that people study.At present, three kinds of method preparations are usually adopted to have germ resistance silastic material.The first carries out surface modification to preformed polymkeric substance, as patent of invention " method on the surface of the goods be made up of silastic material for antimicrobial treatment " (publication number CN102905524A), by under high frequency electromagnetic radiation, process in low-temperature oxygen plasma comes the surface of modified organic silicon rubber item, then by being embedded with silver or/and the bentonitic nano-dispersed powder antibiotic preparation of cupric ion is applied to modified surface process described modified surface, the described surface of described goods forms antimicrobial coating.The method operation is comparatively simple, and easily promote, portioned product achieves suitability for industrialized production, but product antibacterial time is short.The second is polymkeric substance design and synthesis skeleton with antibacterial group, mostly adopts crosslinking technology.As adopted UV-light hydrophilic modifying method at silastic surface grafting hydrophilic polymer PEG1000 and Surfactant OP-10 in journal article " the antibacterial adhesive capacity after medical grade silicon rubber UV-light hydrophilic modifying ", and Contact-angle measurement and the experiment of streptococcus aureus Combined culture are done to modified silastic surface.Good wetting ability can be obtained after silastic material surface modification, and the bacterial adhesion on its surface can be reduced.Crosslinking technology research not only effectively can improve the biocompatibility of silicon rubber, and be connected on the hydroaropic substance retention time of Silica Surface by chemical bond-linking can be longer, but its complex process, fails to promote.Last one is filler antimicrobial silicon rubber, is to add in silicone rubber material by the antiseptic-germicide with antimicrobial component as quaternary ammonium compound, microbiotic, silver ions etc., obtains correlated product.As in patent of invention " organic silicon rubber material of long acting antibiotic and preparation method " (publication number CN102260410A), the antiseptic-germicide and organic solvent with anti-microbial activity are mixed according to volume ratio, then seal and stir and add linking agent vacuumizing and defoaming, drying at room temperature polymerizing curable, obtains the organic silicon rubber material of long acting antibiotic; Organic antibacterial agent sterilization speed is fast, and sterilizing ability is strong, but easily produces resistance.
In daily life, various pathogenic microorganism is widely distributed at occurring in nature, and threatens to HUMAN HEALTH.Intestinal bacteria and streptococcus aureus as modal pathogenic bacterium, once long-standing problem human lives, present stage anti-biotic material germ resistance to detect be also representative mainly with intestinal bacteria and streptococcus aureus.In addition, also have the harm of some malignant bacterias also to cause the concern of people, as Salmonellas, salmonellosis refers to the general name multi-form to the mankind, domestic animal and wild birds and beasts caused by all kinds Salmonellas.Infect the people of Salmonellas or the fecal pollution food of carrier, human hair uncooked food can be made poisoning; In bacterial species food poisoning according to statistics in countries in the world, the normal row umber one of salmonellal food poisoning.Suis often causes suppurative inflammation, toxin disease and allergy disease etc.In addition, global warming, the growth of the environment mould preferably of damp warm, the growing in a large number of mould has a strong impact on HUMAN HEALTH, the using and preserving of product.The present invention, having on the basis of higher sterilizing rate to streptococcus aureus and intestinal bacteria, has good sterilization effect to Salmonellas, suis and mould.
The present invention is directed in the preparation of above antimicrobial silicon rubber, the shortcomings such as the antibacterial time length is short, amalgamation is poor, Mechanical Properties of Silicone Rubber malleable, complicated process of preparation, germ resistance are single, easily develop immunity to drugs, adopt have specific surface area larger, reinforcing good, sterilizing rate is high, environmental protection, make antiseptic-germicide without the antibacterial white cabon black of the characteristics such as resistance, pass through and the abundant fusion of silicon rubber stoste, solidification, obtain antimicrobial silicon rubber.Ensure that higher sterilizing rate, saved cost, processing condition are easy, and keep Mechanical Properties of Silicone Rubber to stablize, broad-spectrum antibacterial property is strong, and application prospect is considerable.
Summary of the invention
The present invention is directed in the preparation of above antimicrobial silicon rubber, the problems such as the antibacterial time length is short, amalgamation is poor, Mechanical Properties of Silicone Rubber malleable, complicated process of preparation, germ resistance are single, easily develop immunity to drugs, provide a kind of preparation method of antimicrobial silicon rubber.
The inventive method is carried out as follows:
(1) water glass solution and saleratus solution are preheated to 70-95 DEG C respectively, mix in the ratio injecting reactor of 1:1.2-1:1.5 by volume, at 70-95 DEG C, abundant stirring reaction 15-30min under 300-500rpm, wherein water glass solution concentration is 5-20wt%, and saleratus solution concentration is 5-15wt%;
(2) ratio of 1:1.2-1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 70-95 DEG C respectively, then the water glass solution after preheating is poured under agitation in the reactant of step (1), drip saleratus solution again, after dripping, 10-30min is reacted at 70-95 DEG C, with acid for adjusting pH value to 2-6, gel antiseptic-germicide is obtained after adding 0.001-1mol/L metal ion liquid reaction 2-10min subsequently, the water glass solution wherein used in this step is the 1/10-7/10 of water glass solution volume in step (1), the ratio that the water glass solution cumulative volume of step (1) and the middle use of step (2) and metal ion liquid amass is 2:1-5:1,
(3) be the ratio of 1:1000-1:20 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the silicon rubber thinner measuring silicon rubber quality 20%-60% add in gel antiseptic-germicide, and dispersion treatment is carried out in mixing; Add in the mixture after dispersion by the silicon rubber of step (3), be stirred to bubble-free, finally poured into by solidifying agent under 300-500rpm, continue to stir 2-5min, whole mixing process vacuumizes, and wherein the addition of solidifying agent is the 2-3% of silicon rubber quality;
B, the silicon rubber thinner measuring silicon rubber quality 20%-60% add in the silicon rubber of step (3), carry out dispersion pre-treatment; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, is stirred to bubble-free under 300-500rpm, finally solidifying agent is poured into, continue to stir 2-5min, whole mixing process vacuumizes, and wherein the addition of solidifying agent is the 2-3% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antimicrobial silicon rubber is taken out and obtains in solidification.
Described metal ion liquid is the mixture of one or more in Silver Nitrate, zinc sulfate, copper sulfate, or is the suspension liquid of silver chloride or titanium dioxide.
Described silicon rubber thinner is sherwood oil, end-vinyl polydimethylsiloxane, end-vinyl Polymethyl methacrylate or hexamethyldisiloxane.
Described solidifying agent is silicon boron tackifier, titanic acid ester tackifier, alkyl diethanolamide, Triglycol distearate, amine oxide or acrylate copolymer.
In described step (4) A, dispersion treatment is ultrasonic disperse 5-15min.
Pre-treatment is disperseed to be strong stirring mixed solution 5-15min under 150-300rpm in described step (4) B.
Described silicon rubber is room temperature vulcanized silicone rubber.
Also rare earth ion salts solution can be added in antimicrobial silicon rubber prepared by the present invention, namely 0.001-0.1mol/L rare earth ion salts solution is added again add metal ion liquid reaction 2-10min in step (2) after, obtained gel antiseptic-germicide, wherein the volume ratio 1:1-3:1 of metal ion liquid and rare earth ion salts solution after continuing reaction 0.5-3h; All the other steps are constant.
Described rare earth ion salt is the one in lanthanum nitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate, Dysprosium trinitrate, holmium nitrate, Erbium trinitrate, thulium nitrate, ytterbium nitrate, lutecium nitrate, Yttrium trinitrate, Scium trinitrate.
Time prepared by the described antimicrobial silicon rubber containing rare earth ion, in step (4) A, dispersion treatment is strong stirring mixed solution 5-15min under 150-300rpm.
The inventive method relative to the advantage of prior art and technique effect as follows:
The present invention is directed to the shortcomings such as the antibacterial time length is short, amalgamation is poor, Mechanical Properties of Silicone Rubber malleable, complicated process of preparation, germ resistance are single, easily develop immunity to drugs in the preparation of existing antimicrobial silicon rubber, this antimicrobial silicon rubber adopts the metal ions such as silver, zinc, copper, titanium to be antibacterial ion, pass through colloidal sol---gel method, antibacterial ion is attached in white carbon black carrier and obtains antibacterial gel, then add pretreated silicon rubber stoste, fully merge, solidify the silastic material namely obtaining and there is antibacterial ability; Shown by embodiment, the antimicrobial silicon rubber prepared has good bactericidal properties, can according to the difference of antiseptic-germicide kind, regulate product sterilizing rate, with other antimicrobial silicon rubber phase ratio, processing condition are easy, cost is low, broad-spectrum antibacterial property is strong, and the basis keeping the original mechanical property of silicon rubber has higher germ resistance, and application prospect is considerable.
This product can be widely used in the daily life fields such as silicon rubber mobile phone shell, silicone rubber pad, silicone rubber tube, refrigerator sealed strip, plays antibacterial, the effect of protection human body.
Antibacterial detection: bacterial classification adopts intestinal bacteria, streptococcus aureus, Salmonellas, suis and mould, sterilizing rate adopts the film applicator coating of the particular requirement of antibacterial, degerming, the purification function anti-biotic material of GB21551.2-2010 family expenses and similar applications electrical equipment to carry out antibacterial detection.
Embodiment
Below by embodiment, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1: the preparation method of this zinc system antimicrobial silicon rubber is as follows:
(1) constant temperature stirring reaction device (vacuum-pumping) is put up, bath temperature is 90 DEG C, water glass solution and saleratus solution are preheated to 90 DEG C respectively, mix in the ratio injecting reactor of 1:1.25 by volume, abundant stirring reaction 15min under 400rpm, wherein water glass solution concentration is 15wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.25 measures water glass solution and saleratus solution respectively by volume, and be preheated to 90 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 150rpm agitation condition, drip saleratus solution again, after dripping, 15min is reacted at 90 DEG C, by sulfuric acid adjust ph to 5, gel antiseptic-germicide is obtained after adding 0.5mol/L solution of zinc sulfate reaction 3h subsequently, the water glass solution wherein used in this step is 1/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of solution of zinc sulfate volume are 3:1,
(3) be the ratio of 1:200 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the sherwood oil measuring silicon rubber quality 60% adds in gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; Add in the mixture after dispersion by the silicon rubber of step (3), stir at 500 rpm and vacuumize 15min to bubble-free, finally poured into by silicon boron tackifier, continue to stir 2min, wherein the addition of silicon boron tackifier is 2% of silicon rubber quality;
B, whole mixing process vacuumize, and the sherwood oil measuring silicon rubber quality 60% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Mixed with the gel antiseptic-germicide of step (2) by mixture after dispersion, stir at 500 rpm and be evacuated to bubble-free, finally poured into by silicon boron tackifier, continue to stir 2min, wherein the addition of silicon boron tackifier is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, after solidification 24h, take out and obtain shaping zinc system antimicrobial silicon rubber.
Following blank sample refers to the experiment contrast sample not adding any material.
Following silicon rubber sample refers to that silicon rubber making step is as embodiment 1, in step (2), does not add any metal ion solution with anti-microbial property.
The anti-microbial property of antibacterial tests to product is utilized to study.Experimentation is as follows: boiling solid medium (peptone 10g, extractum carnis 5g, sodium-chlor 5g, agar 17.5g, distilled water 1000ml), pour in Erlenmeyer flask, through pressure steam sterilizer high pressure (120 DEG C, 1.5MPa) be dispensed into while hot in culture dish after sterilization 20min, cool under aseptic condition, obtain solid medium.
The silicone rubber plate to be detected of clip (50 ± 2) mm × (50 ± 2) mm and control sample, sanitation-grade high density polyethylene(HDPE), is of a size of (50 ± 2) mm × (50 ± 2) mm.Polyethylene film, thickness is 0.05-0.1mm, is of a size of (40 ± 2) mm × (40 ± 2) mm.To used laboratory sample, control sample, mulch film 70% alcohol solution dipping, takes out after 1min, and with aseptic water washing, that should not sterilize with thimerosal as sample directly can use aseptic water washing.Other laboratory apparatuss high-temperature sterilizing chambers 121 DEG C of sterilizing 20min.Control sample and laboratory sample are placed in sterilized plane ware, get the bacterium drop that 1.0 ± 0.1ml configured respectively and be added on sample and test sample, often organize preparation three Duplicate Samples.With tweezers, mulch film is attached on sample and laboratory sample, ensures that bacterium liquid is dispersed on control sample and laboratory sample uniformly.Carry out numbering, plane ware is put into the constant incubator of 37 DEG C, cultivate 24h.
All samples is taken out after 24h, the phosphate buffer soln after 100ml sterilizing is added respectively as elutriant (2.83g disodium hydrogen phosphate,anhydrous in the bottle filling sample, 1.36g potassium hydrogen phosphate, 1000ml distilled water, adjustment pH is 7.0-7.2), repeatedly clean sample, mulch film, be positioned on vibrator, fully shake up, fully vibrate under the rotating speed of 200rpm 30min.After leaving standstill, do gradient dilution to 1 × 10
3~ 5 × 10
3cfuml
-1, bacterium liquid is inoculated on solid medium, and coated plate is even.Solid medium is upside down in incubator, at 37 DEG C, cultivates 18-24h.Through cultivate after, forms bacterium colony by individual cells growth and breeding, statistics colony count, can calculate in sample contain bacterium number.More blank sample contains bacterium number with detection sample, obtains sterilizing rate.Sterilizing rate the results are shown in Table 1, and mechanical property is in table 2.
Table 1
Table 2
。
Embodiment 2: the preparation method of this zinc system antimicrobial silicon rubber is as follows:
(1) constant temperature stirring reaction device (vacuum-pumping) is put up, bath temperature is 85 DEG C, water glass solution and saleratus solution are preheated to 85 DEG C respectively, mix in the ratio injecting reactor of 1:1.3 by volume, abundant stirring reaction 15min at 450 rpm, wherein water glass solution concentration is 12wt%, and saleratus solution concentration is 9wt%;
(2) ratio of 1:1.3 measures water glass solution and saleratus solution respectively by volume, and be preheated to 85 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 100rpm agitation condition, drip saleratus solution again, after dripping, 20min is reacted at 85 DEG C, by sulfuric acid adjust ph to 6, gel antiseptic-germicide is obtained after adding 0.8mol/L solution of zinc sulfate reaction 1h subsequently, the water glass solution wherein used in this step is 3/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of solution of zinc sulfate volume are 2:1,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the end-vinyl polydimethylsiloxane measuring silicon rubber quality 60% adds in gel antiseptic-germicide and mixes, and carry out ultrasonic 10min dispersion treatment; Add in the mixture after dispersion by the silicon rubber of step (3), stir and be evacuated to bubble-free, finally poured into by titanic acid ester tackifier under 400rpm, continue to stir 2min, wherein the addition of titanic acid ester tackifier is 2% of silicon rubber quality;
B, whole mixing process vacuumize, the end-vinyl polydimethylsiloxane measuring silicon rubber quality 60% directly adds in the silicon rubber measured in step (3), under 150rpm, strong stirring mixed solution 10min carries out dispersion pre-treatment, mixture after dispersion is mixed with the gel antiseptic-germicide of step (2), stir at 500 rpm and be evacuated to bubble-free, finally poured into by titanic acid ester tackifier, continue to stir 2min, wherein the addition of titanic acid ester tackifier is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping zinc system antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of the present embodiment zinc system antimicrobial silicon rubber, the results are shown in Table 3, mechanics properties testing is in table 4:
Table 3
Table 4
。
Embodiment 3: the preparation method of this copper system antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 80 DEG C respectively, mix in the ratio injecting reactor of 1:1.5 by volume, at 80 DEG C, abundant stirring reaction 15min under 400rpm, wherein water glass solution concentration is 20wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 80 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 200rpm agitation condition, drip saleratus solution again, after dripping, 15min is reacted at 80 DEG C, by sulfuric acid adjust ph to 5, gel antiseptic-germicide is obtained after adding 0.05mol/L copper-bath reaction 2.5h subsequently, the water glass solution wherein used in this step is 2/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of copper-bath volume are 3:1,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the end-vinyl Polymethyl methacrylate measuring silicon rubber quality 60% adds in gel antiseptic-germicide and mixes, and carry out ultrasonic 10min dispersion treatment; Add in the mixture after dispersion by the silicon rubber of step (3), stir at 500 rpm and be evacuated to bubble-free, finally poured into by alkyl diethanolamide, continue to stir 3min, wherein the addition of solidifying agent is 2% of silicon rubber quality;
B, whole mixing process vacuumize, and the end-vinyl Polymethyl methacrylate measuring silicon rubber quality 60% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, stir at 500 rpm and be evacuated to bubble-free, finally poured into by solidifying agent, continue to stir 3min, wherein the addition of solidifying agent is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping copper system antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of Cu-RE system antimicrobial silicon rubber, the results are shown in Table 5, mechanics properties testing is in table 6:
Table 5
Table 6
。
Embodiment 4: this silver is that the preparation method of antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 90 DEG C respectively, mix in the ratio injecting reactor of 1:1.5 by volume, at 90 DEG C, abundant stirring reaction 15min under 300rpm, wherein water glass solution concentration is 15wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 90 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 200rpm agitation condition, drip saleratus solution again, after dripping, 15min is reacted at 90 DEG C, by nitric acid adjust ph to 2, gel antiseptic-germicide is obtained after adding 0.01mol/L silver nitrate solution reaction 2h subsequently, the water glass solution wherein used in this step is 5/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of silver nitrate solution volume are 3:1,
(3) be the ratio of 1:200 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the hexamethyldisiloxane measuring silicon rubber quality 50% add in gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; The silicon rubber of step (3) is added in the mixture after dispersion, stir at 500 rpm and be evacuated to bubble-free, finally Triglycol distearate is poured into, continue to stir 3min, whole mixing process vacuumizes, and wherein the addition of solidifying agent is 2% of silicon rubber quality;
B, whole mixing process vacuumize, and the hexamethyldisiloxane measuring silicon rubber quality 50% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 300 rpm; Mixture after dispersion is joined in the gel antiseptic-germicide of step (2), mixing, stirs at 500 rpm and is evacuated to bubble-free, finally poured into by Triglycol distearate, continue to stir 3min, wherein the addition of Triglycol distearate is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping silver system antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect that silver is antimicrobial silicon rubber, the results are shown in Table 7, mechanics properties testing is in table 8:
Table 7
Table 8
。
Embodiment 5: this silver is that the preparation method of antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 75 DEG C respectively, mix in the ratio injecting reactor of 1:1.4 by volume, at 75 DEG C, abundant stirring reaction 15min under 300rpm, wherein water glass solution concentration is 20wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.25 measures water glass solution and saleratus solution respectively by volume, and be preheated to 75 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 150rpm agitation condition, drip saleratus solution again, after dripping, 30min is reacted at 75 DEG C, by nitric acid adjust ph to 2, gel antiseptic-germicide is obtained after adding 0.05mol/L silver nitrate solution reaction 1.5h subsequently, the water glass solution wherein used in this step is 2/10 of water glass solution volume in step (1), the ratio that the water glass solution cumulative volume of step (1) and the middle use of step (2) and metal ion liquid amass is 2:1,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the sherwood oil measuring silicon rubber quality 40% adds in gel antiseptic-germicide and mixes, and carry out ultrasonic 15min dispersion treatment; Add in the mixture after dispersion by the silicon rubber of step (3), stir at 500 rpm and be evacuated to bubble-free, finally poured into by amine oxide, continue to stir 4min, wherein the addition of amine oxide is 2% of silicon rubber quality;
B, the sherwood oil measuring silicon rubber quality 40% add in the silicon rubber of step (3), carry out dispersion pre-treatment (under 250rpm strong stirring mixed solution 15min); Mixture after dispersion is joined in the gel antiseptic-germicide of step (2), mixing, stir at 500 rpm and be evacuated to bubble-free, finally amine oxide is poured into, continue to stir 4min, whole mixing process vacuumizes, and wherein the addition of amine oxide is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping silver system antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect that silver is antimicrobial silicon rubber, the results are shown in Table 9, mechanics properties testing is in table 10:
Table 9
Table 10
。
Embodiment 6: the preparation method of this Silver Nitrate and zinc sulfate mixing antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 85 DEG C respectively, mix in the ratio injecting reactor of 1:1.5 by volume, at 85 DEG C, abundant stirring reaction 15min under 500rpm, wherein water glass solution concentration is 20wt%, and saleratus solution concentration is 15wt%;
(2) ratio of 1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 85 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 200rpm agitation condition, drip saleratus solution again, after dripping, 10min is reacted at 85 DEG C, by nitric acid adjust ph to 4, add subsequently after 0.01mol/L metal ion liquid (Silver Nitrate and zinc sulfate is the rear obtained solution of 3:7 ratio mixing in mass ratio) reacts 2h and obtain gel antiseptic-germicide, the water glass solution wherein used in this step is 3/10 of water glass solution volume in step (1), the ratio that the water glass solution cumulative volume of step (1) and the middle use of step (2) and metal ion liquid amass is 2:1,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the end-vinyl polydimethylsiloxane measuring silicon rubber quality 60% adds in gel antiseptic-germicide, and dispersion treatment (ultrasonic 10min) is carried out in mixing; Add in the mixture after dispersion by the silicon rubber of step (3), stir and be evacuated to bubble-free, finally poured into by acrylate copolymer card ripple 940 under 350rpm, continue to stir 2min, wherein the addition of card ripple 940 is 3% of silicon rubber quality;
B, the end-vinyl polydimethylsiloxane measuring silicon rubber stock solution quality 60% add in the silicon rubber of step (3), carry out dispersion pre-treatment (under 300rpm strong stirring mixed solution 5min); Mixture after dispersion is joined in the gel antiseptic-germicide of step (2), mixing, stir at 300 rpm and be evacuated to bubble-free, finally acrylate copolymer card ripple 940 is poured into, continue to stir 2min, whole mixing process vacuumizes, and wherein the addition of card ripple 940 is 3% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping silver-colored zinc mixing antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of silver-colored zinc mixing antimicrobial silicon rubber, the results are shown in Table 11, mechanics properties testing is in table 12:
Table 11
Table 12
。
Embodiment 7: the preparation method of this silver chloride antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 90 DEG C respectively, mix in the ratio injecting reactor of 1:1.5 by volume, at 90 DEG C, abundant stirring reaction 20min under 400rpm, wherein water glass solution concentration is 20wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 90 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 200rpm agitation condition, drip saleratus solution again, after dripping, 20min is reacted at 90 DEG C, by acid+nitric acid adjust ph to 2, gel antiseptic-germicide is obtained after adding 0.02mol/L silver chloride suspension liquid reaction 2h subsequently, the water glass solution wherein used in this step is 1/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of silver chloride suspension liquid volume are 2:1,
(3) be the ratio of 1:300 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the end-vinyl polydimethylsiloxane measuring silicon rubber stock solution quality 60% add in gel antiseptic-germicide, and dispersion treatment (ultrasonic 12min) is carried out in mixing; The silicon rubber of step (3) is added in the mixture after dispersion, stir at 450 rpm and be evacuated to bubble-free, finally silicon boron tackifier are poured into, continue to stir 2min, whole mixing process vacuumizes, and wherein the addition of silicon boron tackifier is 3% of silicon rubber quality;
B, whole mixing process vacuumize, and the end-vinyl Polymethyl methacrylate measuring silicon rubber quality 60% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, stir at 450 rpm and be evacuated to bubble-free, finally poured into by silicon boron tackifier, continue to stir 2min, wherein the addition of solidifying agent is 3% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping silver chloride antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of silver chloride antimicrobial silicon rubber, the results are shown in Table 13, mechanics properties testing is in table 14:
Table 13
Table 14
。
Embodiment 8: the preparation method of this titanium dioxide antibiotic silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 95 DEG C respectively, mix in the ratio injecting reactor of 1:1.4 by volume, at 95 DEG C, abundant stirring reaction 20min under 350rpm, wherein water glass solution concentration is 10wt%, and saleratus solution concentration is 5wt%;
(2) ratio of 1:1.4 measures water glass solution and saleratus solution respectively by volume, and be preheated to 95 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 100rpm agitation condition, drip saleratus solution again, after dripping, 15min is reacted at 95 DEG C, by nitric acid adjust ph to 4, obtained gel antiseptic-germicide after adding the anti-1h of 1mol/L titanium dioxide suspension liquid subsequently, the water glass solution wherein used in this step is 6/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of titanium dioxide suspension liquid volume are 3:1,
(3) be the ratio of 1:50 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the hexamethyldisiloxane measuring silicon rubber stock solution quality 45% add in gel antiseptic-germicide, and ultrasonic 5min dispersion treatment is carried out in mixing; The silicon rubber of step (3) is added in the mixture after dispersion, stir at 500 rpm and be evacuated to bubble-free, finally titanic acid ester tackifier are poured into, continue to stir 3min, whole mixing process vacuumizes, and wherein the addition of titanic acid ester tackifier is 2.5% of silicon rubber quality;
B, whole mixing process vacuumize, and the hexamethyldisiloxane measuring silicon rubber quality 45% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, stir at 500 rpm and be evacuated to bubble-free, finally poured into by titanic acid ester tackifier, continue to stir 3min, wherein the addition of solidifying agent is 2.5% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping titanium dioxide antibiotic silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of titanium dioxide antibiotic silicon rubber, the results are shown in Table 15, mechanics properties testing is in table 16:
Table 15
Table 16
。
Embodiment 9: the preparation method of this copper-lanthanum antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 90 DEG C respectively, mix in the ratio injecting reactor of 1:1.5 by volume, at 90 DEG C, abundant stirring reaction 15min under 500rpm, wherein water glass solution concentration is 15wt%, and saleratus solution concentration is 5wt%;
(2) ratio of 1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 90 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 200rpm agitation condition, drip saleratus solution again, after dripping, 15min is reacted at 90 DEG C, by nitric acid adjust ph to 6, 0.005mol/L lanthanum nitrate hexahydrate is added again after adding 0.04mol/L copper-bath reaction 5min subsequently, obtained gel antiseptic-germicide after continuing reaction 3h, the water glass solution wherein used in this step is 2/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of copper-bath volume are 3:1, the volume ratio 1:1 of copper-bath and lanthanum nitrate hexahydrate,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the sherwood oil measuring silicon rubber quality 60% add in gel antiseptic-germicide, and dispersion treatment (under 150rpm strong stirring mixed solution 15min) is carried out in mixing; The silicon rubber stoste of step (3) is added in the mixture after dispersion, at 500 rpm stir and vacuum filtration to bubble-free; Finally poured into by alkyl diethanolamide, continue to stir 3min, wherein the addition of alkyl diethanolamide is 2% of silicon rubber stock solution quality;
B, whole mixing process vacuumize, and the sherwood oil measuring silicon rubber quality 60% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, stir at 500 rpm and be evacuated to bubble-free, finally poured into by alkyl diethanolamide, continue to stir 3min, wherein the addition of solidifying agent is 2% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping copper-lanthanum antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of copper-lanthanum antimicrobial silicon rubber, the results are shown in Table 17, mechanics properties testing is in table 18:
Table 17
Table 18
。
Embodiment 10: the preparation method of this zinc-gadolinium antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 85 DEG C respectively, mix in the ratio injecting reactor of 1:1.4 by volume, at 85 DEG C, abundant stirring reaction 15min under 400rpm, wherein water glass solution concentration is 20wt%, and saleratus solution concentration is 10wt%;
(2) ratio of 1:1.4 measures water glass solution and saleratus solution respectively by volume, and be preheated to 85 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 150rpm agitation condition, drip saleratus solution again, after dripping, 20min is reacted at 85 DEG C, by nitric acid adjust ph to 5, 0.008mol/L Gadolinium trinitrate solution is added again after adding 0.8mol/L solution of zinc sulfate reaction 5min subsequently, obtained gel antiseptic-germicide after continuing reaction 2h, the water glass solution wherein used in this step is 5/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of solution of zinc sulfate volume are 2:1, the volume ratio 2:1 of solution of zinc sulfate and Gadolinium trinitrate solution,
(3) be the ratio of 1:100 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the end-vinyl polydimethylsiloxane measuring silicon rubber quality 40% add in gel antiseptic-germicide, and dispersion treatment (under 200rpm strong stirring mixed solution 10min) is carried out in mixing; The silicon rubber stoste of step (3) is added in the mixture after dispersion, under 400rpm stir and vacuum filtration to bubble-free; Finally poured into by card ripple 941, continue to stir 2min, wherein the addition of card ripple 941 is 2.5% of silicon rubber stock solution quality;
B, whole mixing process vacuumize, and the end-vinyl polydimethylsiloxane measuring silicon rubber quality 40% adds in the silicon rubber of step (3), and strong stirring mixed solution 10min carries out dispersion pre-treatment at 200 rpm; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, stir and be evacuated to bubble-free, finally poured into by card ripple 941 under 400rpm, continue to stir 3min, wherein the addition of card ripple 941 is 2.5% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping zinc-gadolinium antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of zinc-gadolinium antimicrobial silicon rubber, the results are shown in Table 19, mechanics properties testing is in table 20:
Table 19
Table 20
。
The preparation method of embodiment 11: Ben Yin-holmium antimicrobial silicon rubber is as follows:
(1) water glass solution and saleratus solution are preheated to 75 DEG C respectively, mix in the ratio injecting reactor of 1:1.3 by volume, at 75 DEG C, abundant stirring reaction 30min under 300rpm, wherein water glass solution concentration is 5wt%, and saleratus solution concentration is 15wt%;
(2) ratio of 1:1.3 measures water glass solution and saleratus solution respectively by volume, and be preheated to 75 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 100rpm agitation condition, drip saleratus solution again, after dripping, 30min is reacted at 75 DEG C, by nitric acid adjust ph to 2, 0.003mol/L holmium nitrate solution is added again after adding 0.01mol/L silver nitrate solution reaction 5min subsequently, obtained gel antiseptic-germicide after continuing reaction 1h, the water glass solution wherein used in this step is 7/10 of water glass solution volume in step (1), the water glass solution cumulative volume used in step (1) and step (2) and the ratio of silver nitrate solution volume are 5:1, the volume ratio 3:1 of silver nitrate solution and holmium nitrate solution,
(3) be the ratio of 1:500 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, the hexamethyldisiloxane measuring silicon rubber quality 30% add in gel antiseptic-germicide, and dispersion treatment (under 300rpm strong stirring mixed solution 5min) is carried out in mixing; The silicon rubber stoste of step (3) is added in the mixture after dispersion, at 500 rpm stir and vacuum filtration to bubble-free; Finally poured into by alkyl diethanolamide, continue to stir 5min, wherein the addition of alkyl diethanolamide is 3% of silicon rubber stock solution quality;
B, whole mixing process vacuumize, and the hexamethyldisiloxane measuring silicon rubber quality 30% adds in the silicon rubber of step (3), and strong stirring mixed solution 5min carries out dispersion pre-treatment at 300 rpm; Mixture after dispersion is joined in the gel antiseptic-germicide of step (2), mixing, stirs at 500 rpm and is evacuated to bubble-free, finally poured into by alkyl diethanolamide, continue to stir 5min, wherein the addition of alkyl diethanolamide is 3% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stopping vacuumizing, stopping stirring, mixed solution is poured in mould, solidification 24h takes out and obtains shaping silver-holmium antimicrobial silicon rubber.
Adopt colony counting method to carry out antibacterial experiment, method is with embodiment 1, and detect the sterilization effect of silver-holmium antimicrobial silicon rubber, the results are shown in Table 21, mechanics properties testing is in table 22:
Table 21
Table 22
。
Claims (10)
1. a preparation method for antimicrobial silicon rubber, is characterized in that carrying out as follows:
(1) water glass solution and saleratus solution are preheated to 70-95 DEG C respectively, mix in the ratio injecting reactor of 1:1.2-1:1.5 by volume, at 70-95 DEG C, abundant stirring reaction 15-30min under 300-500rpm, wherein water glass solution concentration is 5-20wt%, and saleratus solution concentration is 5-15wt%;
(2) ratio of 1:1.2-1:1.5 measures water glass solution and saleratus solution respectively by volume, and be preheated to 70-95 DEG C respectively, then the water glass solution after preheating is poured in the reactant of step (1) under 100-200rpm agitation condition, drip saleratus solution again, after dripping, 15-30min is reacted at 70-95 DEG C, with acid for adjusting pH value to 2-6, gel antiseptic-germicide is obtained after adding 0.001-1mol/L metal ion liquid reaction 0.5-3h subsequently, the water glass solution wherein used in this step is the 1/10-7/10 of water glass solution volume in step (1), the ratio that the water glass solution cumulative volume of step (1) and the middle use of step (2) and metal ion liquid amass is 2:1-5:1,
(3) be the ratio of 1:1000-1:20 in the mass ratio of gel antiseptic-germicide and silicon rubber, take silicon rubber, for subsequent use;
(4) step (2) gel antiseptic-germicide and step (3) silicon rubber adopt in A, B two kinds of techniques any one mix:
A, whole mixing process vacuumize, and the silicon rubber thinner measuring silicon rubber quality 20%-60% adds in gel antiseptic-germicide, and dispersion treatment is carried out in mixing; Add in the mixture after dispersion by the silicon rubber of step (3), be stirred to bubble-free, finally poured into by solidifying agent under 300-500rpm, continue to stir 2-5min, wherein the addition of solidifying agent is the 2-3% of silicon rubber quality;
B, whole mixing process vacuumize, and the silicon rubber thinner measuring silicon rubber quality 20%-60% adds in the silicon rubber of step (3), carries out dispersion pre-treatment; Join in the gel antiseptic-germicide of step (2) by the mixture after dispersion, mixing, is stirred to bubble-free, is finally poured into by solidifying agent under 300-500rpm, and continue to stir 2-5min, wherein the addition of solidifying agent is the 2-3% of silicon rubber quality;
(5) when not having bubble to overflow in step (4) mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antimicrobial silicon rubber is taken out and obtains in solidification.
2. the preparation method of antimicrobial silicon rubber according to claim 1, is characterized in that: metal ion liquid is the mixture of one or more in Silver Nitrate, zinc sulfate, copper sulfate, or is the suspension liquid of silver chloride or titanium dioxide.
3. the preparation method of antimicrobial silicon rubber according to claim 1 or 2, is characterized in that: silicon rubber thinner is sherwood oil, end-vinyl polydimethylsiloxane, end-vinyl Polymethyl methacrylate or hexamethyldisiloxane.
4. the preparation method of antimicrobial silicon rubber according to claim 3, is characterized in that: solidifying agent is silicon boron tackifier, titanic acid ester tackifier, alkyl diethanolamide, Triglycol distearate, amine oxide or acrylate copolymer.
5. the preparation method of antimicrobial silicon rubber according to claim 1, is characterized in that: in step (4) A, dispersion treatment is ultrasonic disperse 5-15min.
6. the preparation method of antimicrobial silicon rubber according to claim 1, is characterized in that: disperse pre-treatment to be strong stirring mixed solution 5-15min under 150-300rpm in step (4) B.
7. the preparation method of antimicrobial silicon rubber according to claim 1, is characterized in that: described silicon rubber is room temperature vulcanized silicone rubber.
8. the preparation method of antimicrobial silicon rubber described in claim 1, it is characterized in that: after adding metal ion liquid reaction 2-10min in step (2), add 0.001-0.1mol/L rare earth ion salts solution again, obtained gel antiseptic-germicide, wherein the volume ratio 1:1-3:1 of metal ion liquid and rare earth ion salts solution after continuing reaction 0.5-3h.
9. the preparation method of antimicrobial silicon rubber according to claim 8, is characterized in that: rare earth ion salt is the one in lanthanum nitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate, Dysprosium trinitrate, holmium nitrate, Erbium trinitrate, thulium nitrate, ytterbium nitrate, lutecium nitrate, Yttrium trinitrate, Scium trinitrate.
10. the preparation method of antimicrobial silicon rubber according to claim 8, it is characterized in that: time prepared by the antimicrobial silicon rubber containing rare earth ion, in step (4) A, dispersion treatment is strong stirring mixed solution 5-15min under 150-300rpm.
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| CN105949787A (en) * | 2016-06-06 | 2016-09-21 | 凤阳加松新型材料科技有限公司 | Anti-ageing antibacterial dough kneading pad |
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| CN108774356A (en) * | 2018-06-19 | 2018-11-09 | 昆明理工大学 | A kind of preparation method of antibiotic plastic |
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| CN117534962A (en) * | 2023-09-27 | 2024-02-09 | 广东阿普邦新材料科技股份有限公司 | Wear-resistant antibacterial silica gel and preparation method thereof |
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| CN105949787A (en) * | 2016-06-06 | 2016-09-21 | 凤阳加松新型材料科技有限公司 | Anti-ageing antibacterial dough kneading pad |
| CN105907099A (en) * | 2016-06-27 | 2016-08-31 | 林春梅 | Antibacterial catheter material and preparing method thereof |
| CN108651450A (en) * | 2018-05-02 | 2018-10-16 | 合肥市晨雷思建筑材料科技有限公司 | A kind of composition for the processing of hearing aid surface long-acting bacteriostatic |
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| CN110698803A (en) * | 2018-07-10 | 2020-01-17 | 纳米及先进材料研发院有限公司 | Bacterium-repellent elastomer |
| CN109957251A (en) * | 2019-03-21 | 2019-07-02 | 江西双龙硅材料科技有限公司 | A kind of preparation method of rubber compound |
| CN109957251B (en) * | 2019-03-21 | 2021-07-20 | 江西双龙硅材料科技有限公司 | Preparation method of rubber compound |
| CN110591380A (en) * | 2019-10-10 | 2019-12-20 | 广州赫尔普化工有限公司 | Antibacterial silicone rubber composite material and preparation method thereof |
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