CN112174987B - Soluble silver ion-containing polymerizable monomer, preparation method thereof, silver-containing polymer and antibacterial coating - Google Patents
Soluble silver ion-containing polymerizable monomer, preparation method thereof, silver-containing polymer and antibacterial coating Download PDFInfo
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- CN112174987B CN112174987B CN202011084834.7A CN202011084834A CN112174987B CN 112174987 B CN112174987 B CN 112174987B CN 202011084834 A CN202011084834 A CN 202011084834A CN 112174987 B CN112174987 B CN 112174987B
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- ion
- polymerizable monomer
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- 239000004332 silver Substances 0.000 title claims abstract description 61
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 61
- 239000000178 monomer Substances 0.000 title claims abstract description 60
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 21
- -1 silver ions Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010668 complexation reaction Methods 0.000 claims abstract description 8
- 150000005837 radical ions Chemical class 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 4
- 230000000536 complexating effect Effects 0.000 claims abstract description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- PQCHENNROHVIHO-UHFFFAOYSA-M silver;2-methylprop-2-enoate Chemical compound [Ag+].CC(=C)C([O-])=O PQCHENNROHVIHO-UHFFFAOYSA-M 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 25
- SJNNZXIPFSRUJB-UHFFFAOYSA-N 4-[2-[2-[2-(4-formylphenoxy)ethoxy]ethoxy]ethoxy]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OCCOCCOCCOC1=CC=C(C=O)C=C1 SJNNZXIPFSRUJB-UHFFFAOYSA-N 0.000 description 16
- 229910001961 silver nitrate Inorganic materials 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000000725 suspension Substances 0.000 description 7
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 101150065749 Churc1 gene Proteins 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 102100038239 Protein Churchill Human genes 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- DOMYACLHQZSAAI-UHFFFAOYSA-M silver;carbamimidothioate;prop-2-enoic acid Chemical group [Ag+].NC([S-])=N.OC(=O)C=C DOMYACLHQZSAAI-UHFFFAOYSA-M 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229920002118 antimicrobial polymer Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- UEJSSZHHYBHCEL-UHFFFAOYSA-N silver(1+) sulfadiazinate Chemical class [Ag+].C1=CC(N)=CC=C1S(=O)(=O)[N-]C1=NC=CC=N1 UEJSSZHHYBHCEL-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the field of high molecular compounds obtained by utilizing carbon-carbon unsaturated bond reaction, in particular to a soluble silver-ion-containing polymerizable monomer, a preparation method thereof, a silver-containing polymer and an antibacterial coating. The soluble silver ion-containing polymerizable monomer is soluble in water or organic solvent and has the structure A (AgL n ) x The method comprises the steps of carrying out a first treatment on the surface of the Wherein L is a ligand capable of complexing with silver, n is the number of ligands, A is acid radical ion, and x is the number of acid radical negative charges; A. at least one of L contains a carbon-carbon double bond. The soluble silver ion-containing polymerizable monomer of the present invention is prepared by complexation, and silver ions are bound to carbon-carbon unsaturated bonds in covalent bond or ionic bond. The polymerizable monomer can be dissolved in water or an organic solvent, and can conveniently obtain the silver ion-containing aqueous solution coating, the silver ion-containing organic solvent coating or the silver ion-containing emulsion coating in a homo-polymerization or copolymerization mode.
Description
Technical Field
The invention belongs to the field of high molecular compounds obtained by utilizing carbon-carbon unsaturated bond reaction, and particularly relates to a soluble silver ion-containing polymerizable monomer, a preparation method thereof, a silver-containing polymer and an antibacterial coating.
Background
Silver has long been recognized for its bactericidal effect, and various tableware and jewelry made of silver have been made to eliminate attack by harmful microorganisms. Silver has been expanded to the form of nano silver and silver ions in sterilization applications at present. Nanosilver is a highly dispersed form of elemental silver, typically stored in suspension or powder form. Most of the silver ions are used in the form of inorganic salts of silver, such as soluble silver nitrate and sparingly soluble silver acetate and sulfate, and other salts of silver are practically insoluble or sparingly soluble in water, except for the above-mentioned silver nitrate salts and complexes formed from silver ions. Silver can also form silver-containing compounds with certain organics, such as silver sulfadiazine salts, which are useful in wound treatment and sterilization of burns and scalds, but which are also insoluble in water.
The above inorganic and organic salts of nano silver or silver are all small molecular antibacterial agents, and thus they have the disadvantage that they must be compounded with polymer materials in order to form stable materials and to be able to be manufactured into various products. There are many documents reporting and disclosing such techniques, for example:
the Chinese patent application publication No. CN106009618A discloses a modified and enhanced antibacterial polyurethane composite material, wherein nano silver is loaded on graphene and then is blended with polyurethane, so that the composite material has self-cleaning and antifouling properties. The Chinese patent application with publication number of CN103589040A discloses an antibacterial plastic for food, which is prepared by adding silver ion-loaded ferrite oxide compound and other fillers into polyethylene for blending, wherein the antibacterial rate of the antibacterial plastic to escherichia coli and staphylococcus aureus can reach more than 90%, and the antibacterial time is long.
The prior art is to add nano silver, silver oxide and silver ion carrier into polymer to form antibacterial material. Although the method can achieve a certain effect, most of the silver is wrapped in the resin, and only a small part of the silver can be exposed on the surface to act, so that the effective utilization degree of the silver is low; silver exposed on the surface is poor in combination effect with resin, and can be lost with time or scouring by external force, so that the antibacterial effect is reduced.
Disclosure of Invention
The invention aims to provide a soluble silver ion-containing polymerizable monomer which can be used for preparing a silver-containing polymer with silver ions combined with a polymer matrix in a chemical bonding mode, and the bonding force of the silver ions on the silver-containing polymer is good and the silver ions cannot be lost.
A second object of the present invention is to provide a method for preparing the above-mentioned soluble silver ion-containing polymerizable monomer.
The invention also provides the silver-containing polymer and the antibacterial coating.
In order to achieve the above purpose, the technical scheme of the soluble silver ion-containing polymerizable monomer is as follows:
a soluble silver ion-containing polymerizable monomer which is soluble in water or an organic solvent and has the structure shown below:
A(AgL n ) x ；
wherein L is a ligand capable of complexing with silver, and n is the number of ligands;
a is acid radical ion, x is acid radical negative charge number;
A. at least one of L contains a carbon-carbon double bond.
The soluble silver ion-containing polymerizable monomer of the present invention is prepared by complexation, and silver ions are bound to carbon-carbon unsaturated bonds in covalent bond or ionic bond. The polymerizable monomer can be dissolved in water or an organic solvent, and can conveniently obtain the silver ion-containing aqueous solution coating, the silver ion-containing organic solvent coating or the silver ion-containing emulsion coating in a homo-polymerization or copolymerization mode.
The ligand L is one or more selected from ammonia, thiourea, amino acid, sodium thiosulfate, organic primary amine containing carbon-carbon double bond and saturated organic primary amine. The number of carbon atoms of the organic primary amine having a carbon-carbon double bond and the saturated organic primary amine is preferably 2 to 4. The organic primary amine containing carbon-carbon double bond can be allyl amine, and the saturated organic primary amine can be ethylamine, propylamine, n-butylamine, isobutylamine, and the like.
The number n of ligands is generally 2.
The acid radical ion A is one or more selected from inorganic acid radical ion, unsaturated organic acid radical ion containing carbon-carbon double bond and saturated organic acid radical ion. The inorganic acid radical ion is one or more of chloride ion, sulfate ion and carbonate ion. The number of carbon atoms in the organic acid radical ion and the saturated organic acid radical ion containing carbon-carbon double bond is 2-4. Organic acid radical ions containing carbon-carbon double bonds such as acrylic acid radical ions, methacrylic acid radical ions and the like. Saturated organic acid radical ions such as propionate, acetate and the like. When a is a monovalent acid radical ion such as chloride, propionate, acrylate, etc., x=1; when a is a negative divalent acid ion, x=2, and so on.
Preferably, the polymerizable monomer has a structure represented by the following formula (1):
in the formula (1), R is methyl.
Preferably, the polymerizable monomer has a structure represented by the following formula (2):
the preparation method of the soluble silver ion-containing polymerizable monomer comprises the following steps:
a method for preparing a soluble silver ion-containing polymerizable monomer, comprising the steps of: to insoluble Ag x The A salt and the ligand L are subjected to complexation reaction in a solvent.
The preparation method of the soluble silver ion-containing polymerizable monomer has simple preparation process and can realize large-scale industrial production.
Silver acrylate CH which is insoluble 2 Complexation of the =chrooag and ligand L in a solvent to produce a polymerizable monomer of formula (1);
in the formula (1), R is methyl. The polymerizable monomer of the structure of formula (1) is prepared, and the silver-containing complex formed is soluble in water or an organic solvent according to the nature of the ligand.
To insoluble Ag x Carrying out complexation reaction on the A salt and allylamine in a solvent to obtain a polymerizable monomer with a structure shown in a formula (2);
when the polymerizable monomer with the structure of the formula (2) is prepared, common silver nitrate and acid or salt corresponding to acid radical A can be utilized to react so as to realize the edge replacement of the silver nitrate and generate insoluble Ag x And (3) A salt.
The silver-containing polymer has the technical scheme that:
silver-containing polymers formed by homopolymerizing the soluble silver-ion-containing polymerizable monomers described above or copolymerizing with other unsaturated monomers.
The silver ion-containing polymerizable monomer contains a carbon-carbon double bond, can be subjected to homo-polymerization or copolymerization by adopting a method known in the art, and mainly comprises the step of introducing chemically bonded silver ions into a system of a polymer to realize that the silver ions are not lost and the antibacterial performance of the silver ions is permanently exerted.
The aqueous polymerization, the organic solvent polymerization or the emulsion polymerization may be selected according to the solubility of the silver ion-polymerizable monomer. By selecting comonomer, polymerization degree and the like, indexes such as mechanical property, flexibility and the like of the polymer can be regulated and controlled.
The technical scheme of the antibacterial paint provided by the invention is as follows: an antibacterial paint containing the silver-containing polymer.
The paint may contain components such as resin, filler, defoamer, dispersant, etc. depending on the application. The silver-containing polymer can be used as a main resin or a part of the main resin of the paint, and then the antibacterial paint is formed according to the manufacturing mode of the existing paint.
The antibacterial coating adopting the silver-containing polymer has better silver ion activity than nano silver particles or silver oxide particles; silver ions cannot be embedded in the resin, and the utilization rate of the silver ions is high; and the silver ions cannot be lost, and the antibacterial effect is strong and durable.
Detailed Description
Embodiments of the present invention will be further described with reference to the following specific examples.
1. Specific examples of the soluble silver ion-containing polymerizable monomers of the invention
Example 1
The soluble silver ion-containing polymerizable monomer of this example is propyleneSilver acid ammonia complex, which is soluble in water and has the molecular formula: CH (CH) 2 CHCOO[Ag(NH 3 ) 2 ]。
Example 2
The soluble silver ion-containing polymerizable monomer of the embodiment is a silver thiourea acrylate complex, is soluble in water and has a molecular formula of: CH (CH) 2 CHCOO[Ag(SCN 2 H 4 ) 2 ]。
Example 3
The soluble silver ion-containing polymerizable monomer of this embodiment is a silver-histidine-acrylate complex, which is soluble in water, and in formula (1), the ligand L is histidine (His), and the molecular formula of the silver-histidine-acrylate complex can be expressed as: CH (CH) 2 CHCOO[Ag(His) 2 ]Wherein the amino group in histidine is complexed with silver.
Example 4
The soluble silver ion-containing polymerizable monomer of the embodiment is silver n-butylamine methacrylate complex, can be dissolved in organic solvents such as acetone, dioxane, DMSO, DMF and the like, and has a molecular formula of CH 2 CH(CH 3 )COO[Ag(NH 2 CH 2 CH 2 CH 2 CH 3 ) 2 ]。
Example 5
The soluble silver ion-containing polymerizable monomer of this example is an allylamine silver chloride complex, soluble in water, and has a molecular formula of [ Ag (NH) 2 CH 2 CHCH 2 ) 2 ]Cl。
Example 6
The soluble silver ion-containing polymerizable monomer of the embodiment is an allylamine silver propionate complex, and can be dissolved in organic solvents such as acetone, dioxane, DMSO, DMF and the like, and the molecular formula is CH 3 CH 2 COO[Ag(NH 2 CH 2 CHCH 2 ) 2 ]。
Example 7
The soluble silver ion-containing polymerizable monomer of the embodiment is an allylamine silver acrylate complex, and can be dissolved in organic solvents such as acetone, dioxane, DMSO, DMF and the like, and the molecular formula is CH 2 CHCOO[Ag(NH 2 CH 2 CHCH 2 ) 2 ]。
2. Specific examples of the method for preparing the soluble silver-ion-containing polymerizable monomer of the present invention
Example 8
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 1, and specifically includes the following steps:
1) Preparing silver nitrate aqueous solution with the concentration of 0.5mol/L, then adding acrylic acid for reaction, wherein the molar ratio of the acrylic acid to the silver nitrate is 1.01:1, generating white precipitate, filtering and washing the white precipitate, and then drying the white precipitate in vacuum at 50 ℃ to obtain silver acrylate with the yield of 95 percent calculated by silver nitrate.
2) Weighing a certain amount of silver acrylate, dropwise adding 2% ammonia water into the silver acrylate in molar quantity, continuously stirring until precipitation and dissolution are carried out during the period to generate silver acrylate ammonia complex with a molecular formula of CH 2 CHCOO[Ag(NH 3 ) 2 ]。
Example 9
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 2, and specifically includes the following steps:
1) Silver acrylate was prepared as in example 8;
2) Weighing a certain amount of silver acrylate, dropwise adding 1% of thiourea aqueous solution with the mass fraction of 30% into the silver acrylate in molar quantity, continuously stirring until precipitation and dissolution are carried out, and generating silver acrylate thiourea complex with the molecular formula of CH 2 CHCOO[Ag(SCN 2 H 4 ) 2 ]。
Example 10
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 3, and specifically includes the following steps:
1) Silver acrylate was prepared as in example 8;
2) Weighing a certain amount of silver acrylate, and adding 3% of the group with the mass fraction of 40% to the total amount by molDropwise adding aqueous ammonia solution into silver acrylate, continuously stirring until precipitation and dissolution are carried out to generate silver acrylate histidine complex with a molecular formula of CH 2 CHCOO[Ag(His) 2 ]。
Example 11
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 4, and specifically includes the following steps:
1) Preparing a silver nitrate aqueous solution with the concentration of 0.5mol/L, then adding methacrylic acid for reaction, wherein the molar ratio of the methacrylic acid to the silver nitrate is 1.01:1, generating white precipitate, filtering and washing the white precipitate, and then drying the white precipitate in vacuum at 50 ℃ to obtain the silver methacrylate with the yield of 91 percent calculated by the silver nitrate.
2) Adding silver methacrylate into ethanol to form a mixed solution with the mass fraction of 20%, dropwise adding n-butylamine into the mixed solution under stirring until precipitation is dissolved to form silver methacrylate n-butylamine complex with the molecular formula of CH 2 CH(CH 3 )COO[Ag(NH 2 CH 2 CH 2 CH 2 CH 3 ) 2 ]。
Example 12
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 5, and specifically includes the following steps:
1) Under the condition of dark light, 0.5mol/L silver nitrate is added into sodium chloride solution to react according to the mol ratio of 1:1, silver chloride precipitate is generated, and the silver chloride precipitate is filtered, washed and dried in vacuum at 50 ℃.
2) Weighing quantitative silver chloride, and adding deionized water to form a suspension with the mass fraction of 20%. Adding 1% excessive allylamine to the suspension by mole, stirring until dissolving to form allylamine chloride silver complex with molecular formula of [ Ag (NH) 2 CH 2 CHCH 2 ) 2 ]Cl。
Example 13
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 6, and specifically includes the following steps:
1) Propionic acid is added into 0.5mol/L silver nitrate aqueous solution to react according to the mol ratio of 1.01:1, silver propionate precipitate is generated, and the silver propionate precipitate is filtered, washed and dried in vacuum at 50 ℃ to obtain 94 percent of yield.
2) Weighing quantitative silver propionate, and adding ethanol to form a suspension with the mass fraction of 30%. Adding 2% excessive allylamine into the suspension by mole, stirring until dissolving to form allylamine silver propionate complex with molecular formula of CH 3 CH 2 COO[Ag(NH 2 CH 2 CHCH 2 ) 2 ]。
Example 14
The preparation method of the soluble silver ion-containing polymerizable monomer of this example is described in the preparation of the soluble silver ion-containing polymerizable monomer of example 7, and specifically includes the following steps:
1) Acrylic acid is added into 0.5mol/L silver nitrate aqueous solution to react according to the mol ratio of 1.01:1, silver acrylate sediment is generated, and the silver acrylate sediment is filtered, washed and dried in vacuum at 50 ℃ to obtain the yield of 95 percent.
2) Weighing a certain amount of silver acrylate, and adding deionized water to form a suspension with the mass fraction of 20%. Adding 1% excessive allylamine to the suspension by mole, stirring until dissolving to form allylamine silver acrylate complex with molecular formula of CH 2 CHCOO[Ag(NH 2 CH 2 CHCH 2 ) 2 ]。
3. Specific examples of silver-containing polymers of the invention
Example 15
The silver-containing polymer of this example was prepared by preparing an aqueous solution of 30% by mass of the silver-ammonia acrylate complex of example 1, then adding potassium persulfate of 2% by mass of the silver-ammonia acrylate complex, heating to 75℃with stirring, and keeping the temperature for 4 hours to obtain an aqueous solution of silver-ion-containing polyacrylic acid.
Example 16
The silver-containing polymer of the example is prepared by dissolving the silver allylamine chloride complex of the example 12 in water to prepare a monomer solution with the mass fraction of 25%, then adding potassium persulfate with the mass fraction of 2% of the silver allylamine chloride complex, stirring and dissolving, heating to 80 ℃, and preserving heat for 4 hours to obtain a silver-ion-containing polyacrylic acid aqueous solution.
Example 17
The silver-containing polymer of this example was prepared by adding 25% by weight of the silver n-butylamine methacrylate complex of example 4 (the same as described below based on the weight of water), 1% Span80 and 2% ammonium persulfate to 500 g of water, stirring at high speed for 30min, and then adding 10% ethyl acrylate dropwise to form an emulsion. Then gradually heating to 75 ℃, and carrying out heat preservation reaction for 5 hours to form silver-containing polymer emulsion.
4. The silver-containing polymer solutions or emulsions of examples 15-17 above can be used as the primary or secondary film-forming material to make an antimicrobial coating.
5. Experimental example
The silver-containing polymer solutions or emulsions of examples 15-17 were made into antimicrobial coatings and tested for antimicrobial properties, the results of which are shown in Table 1 below.
TABLE 1 antibacterial Properties of silver-containing polymeric coatings
According to the data of Table 1 above, the antimicrobial polymer coatings made from the silver-containing polymer solutions or emulsions of examples 15-17 have good antimicrobial capabilities. And because silver ions are compounded on the polymer matrix in a chemical bonding mode, the corresponding polymer coating can resist exposure and corrosion of corrosive media, so that the silver ions are prevented from losing and the antibacterial performance of the silver ions is permanently exerted.
Claims (8)
1. A soluble silver ion-containing polymerizable monomer, which is soluble in water or an organic solvent, having the structure shown below:
A(AgL n ) x ；
wherein L is a ligand capable of complexing with silver, and n is the number of ligands;
a is acid radical ion, x is acid radical negative charge number;
A. at least one of L contains a carbon-carbon double bond;
the ligand L is one or more selected from ammonia, thiourea, histidine, n-butylamine and allylamine;
the acid radical ion A is one or more selected from chloride ion, propionate, acrylate and methacrylate ion.
2. The soluble silver-ion containing polymerizable monomer according to claim 1, which has a structure represented by the following formula (1):
in the formula (1), R is methyl.
3. The soluble silver-ion containing polymerizable monomer according to claim 1, which has a structure represented by the following formula (2):
4. a process for preparing a soluble silver-ion containing polymerizable monomer according to any one of claims 1 to 3, comprising the steps of: to insoluble Ag x The A salt and the ligand L are subjected to complexation reaction in a solvent.
5. The method for preparing a soluble silver ion-containing polymerizable monomer according to claim 4, wherein insoluble silver methacrylate CH 2 Complexation of the =chrooag and ligand L in a solvent to produce a polymerizable monomer of formula (1);
in the formula (1), R is methyl.
6. The method for preparing a soluble silver-ion polymerizable monomer according to claim 4, wherein insoluble Ag is x Carrying out complexation reaction on the A salt and allylamine in a solvent to obtain a polymerizable monomer with a structure shown in a formula (2);
7. a silver-containing polymer formed from the homopolymerization of the soluble silver-ion-containing polymerizable monomer of any one of claims 1-3 or copolymerization with other unsaturated monomers.
8. An antimicrobial coating comprising the silver-containing polymer of claim 7.
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| CN109563106A (en) * | 2016-08-09 | 2019-04-02 | 柯达公司 | Silver ion carboxylate radical kiber alkyl amine complex compound |
| CN111484421A (en) * | 2020-04-29 | 2020-08-04 | 洛阳冠银生物科技有限公司 | Antibacterial silver ion compound, non-irritant silver ion antibacterial agent and preparation method and application thereof |
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| CN109563106A (en) * | 2016-08-09 | 2019-04-02 | 柯达公司 | Silver ion carboxylate radical kiber alkyl amine complex compound |
| CN111484421A (en) * | 2020-04-29 | 2020-08-04 | 洛阳冠银生物科技有限公司 | Antibacterial silver ion compound, non-irritant silver ion antibacterial agent and preparation method and application thereof |
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