CN105238056A - Preparation method of antibiosis high temperature silicone rubber - Google Patents
Preparation method of antibiosis high temperature silicone rubber Download PDFInfo
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- CN105238056A CN105238056A CN201510644904.2A CN201510644904A CN105238056A CN 105238056 A CN105238056 A CN 105238056A CN 201510644904 A CN201510644904 A CN 201510644904A CN 105238056 A CN105238056 A CN 105238056A
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- silicone rubber
- high temperature
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- rubber
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 168
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 230000003115 biocidal effect Effects 0.000 title abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 66
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims description 194
- 230000000844 anti-bacterial effect Effects 0.000 claims description 98
- 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
- 239000000203 mixture Substances 0.000 claims description 53
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 238000005987 sulfurization reaction Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- -1 polydimethylsiloxane Polymers 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 16
- 229910021645 metal ion Inorganic materials 0.000 claims description 15
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 15
- 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
- 238000007711 solidification Methods 0.000 claims description 13
- 230000008023 solidification Effects 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- MOSXLDGILGBOSZ-UHFFFAOYSA-N ethenyl-methyl-phenylsilicon Chemical compound C=C[Si](C)C1=CC=CC=C1 MOSXLDGILGBOSZ-UHFFFAOYSA-N 0.000 claims description 11
- 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
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920000260 silastic Polymers 0.000 claims description 8
- 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 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical group [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 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
- 239000002904 solvent Substances 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate 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
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract description 2
- 206010059866 Drug resistance Diseases 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 38
- 238000004073 vulcanization Methods 0.000 description 34
- 230000000845 anti-microbial effect Effects 0.000 description 19
- 238000005520 cutting process Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000007731 hot pressing Methods 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 8
- 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
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000013068 control sample Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000036039 immunity Effects 0.000 description 4
- 239000006101 laboratory sample Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005267 amalgamation Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002362 mulch Substances 0.000 description 3
- RFYTWKQWFTUQKQ-UHFFFAOYSA-N [Zn].[Gd] Chemical class [Zn].[Gd] RFYTWKQWFTUQKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- FQVNUZAZHHOJOH-UHFFFAOYSA-N copper lanthanum Chemical class [Cu].[La] FQVNUZAZHHOJOH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 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
- 210000000056 organ Anatomy 0.000 description 2
- 238000005086 pumping Methods 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
- 241000208479 Anagallis arvensis Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRYDISAKNPQQOL-UHFFFAOYSA-N [Ag].[Ho] Chemical compound [Ag].[Ho] NRYDISAKNPQQOL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001879 copper Chemical class 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
- 239000013536 elastomeric material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005728 strengthening 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method of antibiosis high temperature 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; and adding corresponding high temperature silicone rubber raw rubber, fully mixing, and vulcanizing to prepare a high temperature silicone rubber material with antibiosis ability, or directly adding high temperature silicon sulfide rubber, fully fusing, and curing to obtain the silicone rubber material with antibiosis ability. The antibiosis high temperature silicone rubber prepared in the invention has the advantages of high temperature resistance, enhancement of the mechanical performances of silicone rubber, high antibiosis, strong antibiosis broad spectrum activity, high sterilization rate, no generation of drug resistance, safety to human bodies and environment, wide uses, and facilitation of the large-scale quantitative production of the future market.
Description
Technical field
The present invention relates to a kind of preparation method of antibacterial high temperature silicone rubber.
Background technology
Silicone rubber products is widely used, and along with improving constantly of standard of living, the market requirement of functional type silicone rubber products is increasing, wherein the field such as industrial production, health care, people's livelihood health care all requires higher, as machine tool, operation instrument, medical treatment product, artificial organ, edible utensil etc. to the germ resistance of silicone rubber products.Silicon rubber, by vulcanization and curing temperature, divides heat vulcanization type (high-temperature silicon disulfide rubber HTV) and room temperature vulcanized (RTV).Be cross-linkable solidifying under room temperature silicon rubber normal temperature, physics normality is fluid or thickness paste, is often used to tackiness agent, sealing agent, protective coating, Embedding Material and low temperature mould processed etc.High temperature silicone rubber physical and mechanical property is excellent, intensity is large, high temperature resistant, corresponding performance can be obtained by adding different additives; Compared to room temperature silicon rubber, high temperature silicone rubber is of many uses, is applicable to the silicone rubber products preparation of various industry.
The development of economic society, people require day by day to improve to the anti-bacteria and anti-virus produced, live.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, and of many uses, eco-friendly inorganic antibacterial is combined with silicon rubber and obtains the focus that antimicrobial silicon elastomeric material becomes this field instantly.At present, mostly there is 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 antimicrobial silicon rubber of manufacture; And the defect such as antibacterial room temperature Mechanical Properties of Silicone Rubber is poor, undercapacity makes its suitability be subject to the restriction of operating environment, cannot meet large-scale productive life demand.
The problem that the present invention is directed in the preparation of above antimicrobial silicon rubber 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, through fully mixing, the sulfuration with high temperature silicone rubber rubber, obtain antibacterial high temperature silicone rubber.Ensure that higher sterilizing rate, enhance broad-spectrum antibacterial property and can not develop immunity to drugs, improve Mechanical Properties of Silicone Rubber, of many uses, application has universality.
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, and the defects such as antibacterial room temperature Mechanical Properties of Silicone Rubber is poor, undercapacity, provide a kind of preparation method of antibacterial high temperature silicone 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 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, the ratio of 100:4-100:7 is by raw-silastic continuously and constitution controller mixing in mass ratio, divide step (2) the gel antiseptic-germicide adding raw-silastic continuously quality 10-40% for 2-5 time in the mixture, then the organic peroxy type vulcanizing agent of raw-silastic continuously quality 0.6%-1.2% is added, at 140-180 DEG C, 2-3h is processed after mixing, then 25-40min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, namely rubber unvulcanizate obtains antibacterial high temperature silicone rubber after carrying out routine two stage sulfurations;
In described two stage sulfurations, one step cure (primary vulcanization) is first by after rubber unvulcanizate cutting, pressing mold, (150-180 DEG C, 10-15MPa) sulfuration 10-15min at high temperature under high pressure; Post vulcanization (postcure) is placed in baking oven by the discharging of primary vulcanization, places 5-7h and obtain antibacterial high temperature silicone rubber at 200-250 DEG C;
B, high-temperature silicon disulfide rubber is joined in solvent, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the silicon rubber thinner measuring high-temperature silicon disulfide rubber quality 20%-60% adds in step (2) gel antiseptic-germicide, and dispersion treatment is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, 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; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone 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 raw-silastic continuously is methyl silicone rubber, methyl vinyl silicone rubber or methyl vinyl phenyl silicon rubber.
In described step (3) A technique, organic peroxy type vulcanizing agent is dicumyl peroxide (DCP), dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di-t-butyl hexane peroxides (DBPMH) or the benzoyl peroxide tertiary butyl (TBPB).
In described step (3) A technique, constitution controller is a kind of in cyclosilazane, Diphenylsilanediol, dimethyldimethoxysil,ne, hexamethyldisilazane, hydroxy silicon oil.
Oil viscosity 10 ~ 30mm at described hydroxy silicon oil refers to 25 DEG C
2/ s, hydroxy radical content are the product of hydroxy silicon oil quality 6 ~ 12%, and such as Chengdu Gracia chemical technology company limited produces, production code member 1008330.
In described step (3) B technique, solvent is normal hexane, hexanaphthene, normal heptane, dimethylbenzene or tetrahydrofuran (THF).
In described step (3) B technique, silicon rubber thinner is sherwood oil, end-vinyl polydimethylsiloxane, end-vinyl Polymethyl methacrylate or hexamethyldisiloxane.
In described step (3) B technique, solidifying agent is silicon boron tackifier, titanic acid ester tackifier, alkyl diethanolamide, Triglycol distearate, amine oxide or acrylate copolymer.
In described step (3) B technique, dispersion treatment is ultrasonic disperse 5-15min.
Also rare earth ion salts solution can be added: after namely adding metal ion liquid reaction 2-10min in step (2), add 0.001-0.1mol/L rare earth ion salts solution again in antibacterial high temperature silicone rubber prepared by the present invention, 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.
The inventive method relative to the advantage of prior art and technique effect as follows:
The present invention is directed to the antibacterial time length in the preparation of existing antimicrobial silicon rubber short, amalgamation is poor, Mechanical Properties of Silicone Rubber malleable, complicated process of preparation, germ resistance is single, easily to develop immunity to drugs and antibacterial room temperature Mechanical Properties of Silicone Rubber is poor, the shortcomings such as undercapacity, this antibacterial high temperature silicone rubber adopts silver, zinc, copper, the metal ions such as titanium are antibacterial ion, pass through colloidal sol---gel method, antibacterial ion is attached in white carbon black carrier and obtains antibacterial gel, then corresponding high temperature silicone rubber rubber is added, fully mixing, back mixing, namely sulfuration obtains the high temperature silicone rubber material with antibacterial ability, shown by embodiment, the antibacterial high temperature silicone 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, broad-spectrum antibacterial property is strong, and the basis strengthening Mechanical Properties of Silicone Rubber has higher germ resistance, of many uses, application has universality.
This product can be widely used in the daily productive life fields such as machine tool, operation instrument, medical treatment product, artificial organ, edible utensil, plays antibacterial, the effect of protection quality product or HUMAN HEALTH.
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: this zinc is that the preparation method of antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicon kautschuk and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:4 in kneader in mass ratio, divide step (2) the gel antiseptic-germicide adding methyl vinyl silicon kautschuk quality 20% for 2 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicon kautschuk quality 0.6% is added, 5-dimethyl-2, 5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 140 DEG C, 2.5h is processed after mixing, then 30min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 160 DEG C, pressure 10MPa, and every 6min exhaust once, post vulcanization (postcure): again the discharging of primary vulcanization is placed in baking oven, places 6h and obtains antibacterial high temperature silicone rubber at 220 DEG C,
B, high-temperature silicon disulfide rubber is joined in normal hexane, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the sherwood oil measuring high-temperature silicon disulfide rubber quality 60% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, under 400rpm, be stirred 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; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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: this zinc is that the preparation method of antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl phenyl silicon rubber and cyclosilazane mix by the ratio of 100:5 in kneader in mass ratio, divide step (2) the gel antiseptic-germicide adding methyl vinyl phenyl silicon rubber quality 30% for 3 times in the mixture, then the organic peroxy type vulcanizing agent dicumyl peroxide of methyl vinyl phenyl silicon rubber quality 0.6% is added, at 150 DEG C, 2h is processed after mixing, then heat 30min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 10min under thermocompressor 180 DEG C, pressure 10MPa, and every 5min exhaust once; Post vulcanization (postcure): again the discharging of primary vulcanization is placed in baking oven, places 7h and obtains antibacterial high temperature silicone rubber at 200 DEG C;
B, high-temperature silicon disulfide rubber is joined in tetrahydrofuran (THF), fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the end-vinyl polydimethylsiloxane measuring high-temperature silicon disulfide rubber quality 60% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, under 400rpm, be stirred 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.When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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: this copper is that the preparation method of antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicone rubber and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:5 in kneader in mass ratio, divide step (2) the gel antiseptic-germicide adding methyl vinyl silicone rubber quality 40% for 4 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicone rubber quality 0.6% is added, 5-dimethyl-2, 5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 150 DEG C, 2h is processed after mixing, then 30min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, rubber unvulcanizate is carried out post vulcanization, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 10min under thermocompressor 160 DEG C, pressure 10MPa, and every 5min exhaust once, post vulcanization (postcure): again the discharging of sulfuration is placed in baking oven, places 6h and obtains antibacterial high temperature silicone rubber at 220 DEG C,
B, methyl vinyl silicon kautschuk is joined in normal hexane, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the end-vinyl polydimethylsiloxane measuring high-temperature silicon disulfide rubber quality 60% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 15min) is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, be stirred to bubble-free, finally poured into by alkyl diethanolamide under 400rpm, continue to stir 3min, wherein the addition of alkyl diethanolamide is 2% of silicon rubber quality.When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicone rubber and Diphenylsilanediol mix by the ratio of 100:6 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl silicone rubber quality 40% for 4 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicone rubber quality 1% is added, 5-dimethyl-2,5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 160 DEG C, 2h is processed after mixing, then heat 25min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 12min under thermocompressor 165 DEG C, pressure 12MPa, and every 5min exhaust once; Post vulcanization (postcure): the discharging of primary vulcanization is placed in baking oven again, places 7h and obtains antibacterial high temperature silicone rubber at 200 DEG C;
B, high-temperature silicon disulfide rubber is joined in hexanaphthene, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the hexamethyldisiloxane measuring high-temperature silicon disulfide rubber quality 50% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 500 rpm, finally poured into by Triglycol distearate, continue to stir 3min, wherein the addition of Triglycol distearate is 2.5% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl silicone rubber and dimethyldimethoxysil,ne mix by the ratio of 100:7 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl silicone rubber quality 30% for 3 times in the mixture, then the organic peroxy type vulcanizing agent dibenzoyl peroxide of methyl silicone rubber quality 0.8% is added, at 180 DEG C, 2h is processed after mixing, then heat 40min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 180 DEG C, pressure 15MPa, and every 5min exhaust once; Post vulcanization (postcure): again the discharging of sulfuration is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 250 DEG C;
B, high-temperature silicon disulfide rubber is joined in dimethylbenzene, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the sherwood oil measuring high-temperature silicon disulfide rubber quality 40% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 15min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 300 rpm, finally poured into by amine oxide, continue to stir 4min, wherein the addition of amine oxide is 3% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 that this Silver Nitrate and zinc sulfate mix antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicone rubber and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:5 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl silicone rubber quality 40% for 5 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicone rubber quality 0.6% is added, 5-dimethyl-2, 5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 160 DEG C, 3h is processed after mixing, then 35min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 150 DEG C, pressure 15MPa, and every 5min exhaust once, post vulcanization (postcure): again the discharging of primary vulcanization is placed in baking oven, places 6h and obtains antibacterial high temperature silicone rubber at 200 DEG C,
B, high-temperature silicon disulfide rubber is joined in normal hexane, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the end-vinyl polydimethylsiloxane measuring high-temperature silicon disulfide rubber quality 60% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 10min) is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, under 350rpm, be stirred to bubble-free, finally poured into by acrylate copolymer card ripple 940, continue to stir 3min, wherein the addition of acrylate copolymer card ripple 940 is 3% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 the antibacterial high temperature silicone rubber of this silver chloride 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl phenyl silicon rubber and hexamethyldisilazane mix by the ratio of 100:4 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl phenyl silicon rubber quality 30% for 3 times in the mixture, then the organic peroxy type vulcanizing agent benzoyl peroxide tertiary butyl of methyl vinyl phenyl silicon rubber quality 1.2% is added, at 170 DEG C, 2h is processed after mixing, then heat 35min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 10min under thermocompressor 175 DEG C, pressure 12MPa, and every 5min exhaust once; Post vulcanization (postcure): again the discharging of primary vulcanization is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 200 DEG C;
B, high-temperature silicon disulfide rubber is joined in tetrahydrofuran (THF), fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the end-vinyl Polymethyl methacrylate measuring high-temperature silicon disulfide rubber quality 25% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 12min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 450 rpm, finally poured into by silicon boron tackifier, continue to stir 2min, wherein the addition of silicon boron tackifier is 3% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicone rubber and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:6 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl silicone rubber 20% for 3 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicone rubber quality 0.9% is added, 5-dimethyl-2, 5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 145 DEG C, 3h is processed after mixing, then 30min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 160 DEG C, pressure 10MPa, and every 5min exhaust once, post vulcanization (postcure): again the discharging of primary vulcanization is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 220 DEG C,
B, high-temperature silicon disulfide rubber is joined in normal heptane, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the hexamethyldisiloxane measuring high-temperature silicon disulfide rubber quality 45% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 5min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 500 rpm, finally poured into by titanic acid ester tackifier, continue to stir 3min, wherein the addition of titanic acid ester tackifier is 2% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 the antibacterial high temperature silicone rubber of this copper-lanthanum 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl silicone rubber and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:6 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl silicone rubber quality 15% for 2 times in the mixture, then the organic peroxy type vulcanizing agent 2 of methyl vinyl silicone rubber quality 1% is added, 5-dimethyl-2, 5-di-t-butyl hexane peroxide (" two 25 " DBPMH), at 160 DEG C, 2h is processed after mixing, then 30min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 160 DEG C, pressure 10MPa, and every 5min exhaust once, post vulcanization (postcure): again the discharging of sulfuration is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 220 DEG C,
B, high-temperature silicon disulfide rubber is joined in normal hexane, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the sherwood oil measuring high-temperature silicon disulfide rubber quality 60% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 15min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 500 rpm, finally poured into by alkyl diethanolamide, continue to stir 3min, wherein the addition of alkyl diethanolamide is 2% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl silicone rubber and Diphenylsilanediol mix by the ratio of 100:4 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl silicone rubber quality 30% for 3 times in the mixture, then the organic peroxy type vulcanizing agent dicumyl peroxide of methyl silicone rubber quality 1.2% is added, at 160 DEG C, 2h is processed after mixing, then heat 30min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 10min under thermocompressor 160 DEG C, pressure 10MPa, and every 5min exhaust once; Post vulcanization (postcure): again the discharging of sulfuration is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 200 DEG C;
B, high-temperature silicon disulfide rubber is joined in tetrahydrofuran (THF), fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the end-vinyl polydimethylsiloxane measuring high-temperature silicon disulfide rubber quality 40% adds in step (2) gel antiseptic-germicide, and dispersion treatment (ultrasonic disperse 5min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 500 rpm, finally poured into by card ripple 941, continue to stir 3min, wherein the addition of card ripple 941 is 2.5% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, methyl vinyl phenyl silicon rubber and hydroxy silicon oil (Chengdu Gracia chemical technology company limited) mix by the ratio of 100:5 in kneader in mass ratio, divide gel antiseptic-germicide in the step (2) adding methyl vinyl phenyl silicon rubber quality 30% for 3 times in the mixture, then the organic peroxy type vulcanizing agent dibenzoyl peroxide of methyl vinyl phenyl silicon rubber quality 0.7% is added, at 150 DEG C, 2h is processed after mixing, then heat 30min under vacuum conditions, be finally cooled to room temperature discharging and obtain rubber unvulcanizate; Rubber unvulcanizate is carried out two stage sulfurations, one step cure (primary vulcanization): take the cutting of 30g rubber unvulcanizate and load in the mould of 100mm × 100mm × 2mm after pressing mold, hot pressing 15min under thermocompressor 165 DEG C, pressure 10MPa, and every 5min exhaust once; Post vulcanization (postcure): again the discharging of sulfuration is placed in baking oven, places 5h and obtains antibacterial high temperature silicone rubber at 200 DEG C;
B, high-temperature silicon disulfide rubber is joined in hexanaphthene, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the hexamethyldisiloxane measuring high-temperature silicon disulfide rubber quality 20% adds in step (2) gel antiseptic-germicide, and dispersion treatment (supersound process 10min) is carried out in mixing; Joined in the mixture after dispersion by high-temperature silicon disulfide rubber solution, be stirred to bubble-free at 500 rpm, finally poured into by alkyl diethanolamide, continue to stir 5min, wherein the addition of alkyl diethanolamide is 3% of silicon rubber quality; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
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 (11)
1. a preparation method for antibacterial high temperature silicone 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) preparation of antibacterial high temperature silicone rubber adopt in A, B two kinds of techniques any one carry out:
A, under normal temperature condition, the ratio of 100:4-100:7 is by raw-silastic continuously and constitution controller mixing in mass ratio, divide step (2) the gel antiseptic-germicide adding raw-silastic continuously quality 10-40% for 2-5 time in the mixture, then the organic peroxy type vulcanizing agent of raw-silastic continuously quality 0.6%-1.2% is added, at 140-180 DEG C, 2-3h is processed after mixing, then 25-40min is heated under vacuum conditions, finally be cooled to room temperature discharging and obtain rubber unvulcanizate, namely rubber unvulcanizate obtains antibacterial high temperature silicone rubber after carrying out two stage sulfurations;
B, high-temperature silicon disulfide rubber is joined in solvent, fully dissolve and form high-temperature silicon disulfide rubber solution; Whole mixing process vacuumizes, and the silicon rubber thinner measuring high-temperature silicon disulfide rubber quality 20-60% adds in step (2) gel antiseptic-germicide, and dispersion treatment is carried out in mixing; Joined by high-temperature silicon disulfide rubber solution in the mixture after dispersion, 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; When not having bubble to overflow in mixed solution, stop vacuumizing, stop stirring, mixed solution is poured in mould, shaping antibacterial high temperature silicone rubber is taken out and obtains in solidification.
2. the preparation method of antibacterial high temperature silicone 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 antibacterial high temperature silicone rubber according to claim 1, is characterized in that: raw-silastic continuously is methyl silicone rubber, methyl vinyl silicone rubber or methyl vinyl phenyl silicon rubber.
4. the preparation method of antibacterial high temperature silicone rubber according to claim 1, it is characterized in that: in step (3) A technique, organic peroxy type vulcanizing agent is dicumyl peroxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide or the benzoyl peroxide tertiary butyl.
5. the preparation method of antibacterial high temperature silicone rubber according to claim 1, is characterized in that: in step (3) A technique, constitution controller is a kind of in cyclosilazane, Diphenylsilanediol, dimethyldimethoxysil,ne, hexamethyldisilazane, hydroxy silicon oil.
6. the preparation method of antibacterial high temperature silicone rubber according to claim 1, is characterized in that: in step (3) B technique, solvent is normal hexane, hexanaphthene, normal heptane, dimethylbenzene or tetrahydrofuran (THF).
7. the preparation method of antibacterial high temperature silicone rubber according to claim 1, is characterized in that: in step (3) B technique, silicon rubber thinner is sherwood oil, end-vinyl polydimethylsiloxane, end-vinyl Polymethyl methacrylate or hexamethyldisiloxane.
8. the preparation method of antibacterial high temperature silicone rubber according to claim 1, is characterized in that: in step (3) B technique, solidifying agent is silicon boron tackifier, titanic acid ester tackifier, alkyl diethanolamide, Triglycol distearate, amine oxide or acrylate copolymer.
9. the preparation method of antibacterial high temperature silicone rubber according to claim 1, is characterized in that: in step (3) B technique, dispersion treatment is ultrasonic disperse 5-15min.
10. the preparation method of antibacterial high temperature silicone 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.
The preparation method of 11. antibacterial high temperature silicone rubber according to claim 10, 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115260411A (en) * | 2022-09-20 | 2022-11-01 | 南通为华创新材料科技有限公司 | Medical composite material and preparation method thereof |
| CN116023784A (en) * | 2021-10-25 | 2023-04-28 | Oppo广东移动通信有限公司 | Antibacterial silicone rubber, silicone rubber product and method thereof, wearing product and antibacterial material |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260410A (en) * | 2011-07-13 | 2011-11-30 | 大连海洋大学 | Long-acting antibacterial organic silicon rubber material and preparation method thereof |
| CN103289408A (en) * | 2012-02-29 | 2013-09-11 | 刘芳 | Method for preparing silicon rubber |
-
2015
- 2015-10-09 CN CN201510644904.2A patent/CN105238056B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260410A (en) * | 2011-07-13 | 2011-11-30 | 大连海洋大学 | Long-acting antibacterial organic silicon rubber material and preparation method thereof |
| CN103289408A (en) * | 2012-02-29 | 2013-09-11 | 刘芳 | Method for preparing silicon rubber |
Non-Patent Citations (3)
| Title |
|---|
| BIN ZHANG等: ""Synthesis characterization,and antimicrobial properties of Cu-inorganic antibacterial material containing lanthanum"", 《JOURNAL OF RARE EARTHS》 * |
| CUIPING MAO等: ""Optimized preparation of zinc-inorganic antibacterial material containing samarium using response surface methodology"", 《JOURNAL OF RARE EARTHS》 * |
| 李欢等: ""掺钆锌型无机抗菌材料的研究"", 《硅酸盐通报》 * |
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