CN115417828A - Antibacterial environment-friendly acrylic acid material and preparation method and application thereof - Google Patents
Antibacterial environment-friendly acrylic acid material and preparation method and application thereof Download PDFInfo
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- CN115417828A CN115417828A CN202210813547.8A CN202210813547A CN115417828A CN 115417828 A CN115417828 A CN 115417828A CN 202210813547 A CN202210813547 A CN 202210813547A CN 115417828 A CN115417828 A CN 115417828A
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- Prior art keywords
- antibacterial
- benzisothiazolinone
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- preferred embodiments
- compound
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 63
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title abstract description 34
- KANAPVJGZDNSCZ-UHFFFAOYSA-N 1,2-benzothiazole 1-oxide Chemical class C1=CC=C2S(=O)N=CC2=C1 KANAPVJGZDNSCZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000002736 metal compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 8
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000976 ink Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 3
- 241000588724 Escherichia coli Species 0.000 abstract description 9
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000001035 drying Methods 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004925 Acrylic resin Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 11
- 238000010992 reflux Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- 229960002887 deanol Drugs 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000012972 dimethylethanolamine Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 150000007530 organic bases Chemical class 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- -1 isothiazolinone compound Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WBDLSXCAFVEULB-UHFFFAOYSA-N acetonitrile;methylsulfinylmethane Chemical compound CC#N.CS(C)=O WBDLSXCAFVEULB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- 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
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
-
- 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
Abstract
The invention discloses an antibacterial environment-friendly acrylic acid material and a preparation method and application thereof
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antibacterial environment-friendly acrylic acid material and a preparation method and application thereof.
Background
The acrylic acid material has the advantages of low price, good heat resistance, high glossiness and the like, and is widely applied to the fields of coatings, printing inks, adhesives and the like. However, most of the traditional acrylic materials are solvent-based, have the defects of high content of volatile organic compounds, large peculiar smell and the like, and have high harm to human bodies and environment. With the enhancement of the environmental protection consciousness of people, the preparation of the environment-friendly acrylic material becomes a research hotspot.
The isothiazolinone compound has an antibacterial function, and can delay the release of the antifouling agent and prolong the antifouling life of the coating. Compared with common bacteriostatic agents such as ammonium borate, low-toxicity phenol, F-101 and the like, the isothiazolinone compound has better environmental protection performance, can be quickly degraded, has low toxicity to organisms, is widely applied to the fields of corrosion prevention, medicines and the like, and can be used as an environment-friendly antifouling agent for antifouling paint.
The benzisothiazolinone has better high-temperature stability and acid and alkali resistance, can adapt to harsh processing environment, and is widely applied to products such as latex products, water-soluble resin, acrylic acid and the like. However, currently, the antibacterial effect achieved by adding benzisothiazolinone to a material by a physical blending method and controlling the release of benzisothiazolinone by hydrolysis of the material is not ideal.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The invention provides an antibacterial environment-friendly acrylic material and a preparation method and application thereof, the invention grafts modified benzisothiazolinone on the environment-friendly acrylic material, and the obtained antibacterial environment-friendly acrylic material has better antibacterial effect on staphylococcus aureus and escherichia coli, improves the antibacterial performance of the environment-friendly acrylic material, has the characteristic of environmental protection, and has good application prospect in the field of paint.
In a first aspect of the invention, there is provided a process for the preparation of a modified benzisothiazolinone, the process comprising the steps of: and (3) reacting the compound I with potassium thiocyanate in a solvent to prepare a compound II, and hydrolyzing the compound II to prepare the modified benzisothiazolinone shown in the formula III.
According to a first aspect of the present invention, in some embodiments of the present invention, the compound I has the formula
In some embodiments of the present invention, X in compound I is selected from any one of F, cl, br and I.
In some preferred embodiments of the invention, compound II has the formula
In some preferred embodiments of the present invention, X in compound ii is selected from any one of F, cl, br, and I.
In some preferred embodiments of the invention, the modified benzisothiazolinone of compound III is of the formula
In some preferred embodiments of the present invention, the molar ratio of compound i to potassium thiocyanate is (4 to 6): (9 to 11).
In some preferred embodiments of the invention, the solvent comprises H 2 O, N, at least one of N-dimethylformamide, dimethylsulfoxide acetonitrile, methanol.
In some preferred embodiments of the invention, a catalyst, a crosslinking agent, and an organic base are also used in the process for preparing the modified benzisothiazolinone.
In some preferred embodiments of the invention, the catalyst comprises CuI, cuBr, cuCl 2 、Cu(OAc) 2 At least one of (1).
In some preferred embodiments of the present invention, the crosslinking agent comprises at least one of Triethylenediamine (TMEDA), dimethylethylenediamine (DMEDA), tetramethylethylenediamine (TMEDA).
In some preferred embodiments of the invention, the organic base comprises 1,4-diazabicyclo [2.2.2]Octane (DABCO), triethylamine (Et) 3 N).
In some preferred embodiments of the invention, compound i: potassium thiocyanate: catalyst: a crosslinking agent: organic base: the molar ratio of the solvent is (4-6): (9-11): (0.5-2): (0.5-2): (1-3): (30 to 70).
In some more preferred embodiments of the invention, compound i: potassium thiocyanate: catalyst: a crosslinking agent: organic base: the molar ratio of the solvent is 5:10:1:1:2:50.
in some preferred embodiments of the invention, the preparation of the modified benzisothiazolinone is carried out in an inert atmosphere.
In some preferred embodiments of the invention, the temperature of the reaction is from 120 ℃ to 160 ℃.
In some preferred embodiments of the present invention, the reaction time is 48 to 72 hours.
In some preferred embodiments of the present invention, compound i and potassium thiocyanate react in a solvent, and are washed with distilled water to remove impurities, and dried under vacuum to obtain compound ii.
In some preferred embodiments of the present invention, the drying temperature is 80 ℃ to 100 ℃.
In some preferred embodiments of the present invention, the drying time is 24 to 72 hours.
In some preferred embodiments of the invention, the method of hydrolyzing the compound ii is hydrolysis using a strong base.
In some preferred embodiments of the invention, the temperature at which the compound II is hydrolyzed is 130 to 160 ℃.
In some preferred embodiments of the invention, the compound II is hydrolyzed at a pressure of 1500 to 2500Pa.
In some preferred embodiments of the invention, the molar ratio of strong base to compound ii is 1:1.
in some preferred embodiments of the invention, the hydrolysis time is between 5 and 6 hours.
In some preferred embodiments of the present invention, compound ii is hydrolyzed and then washed with absolute ethanol to precipitate solids.
In some preferred embodiments of the invention, the precipitated solid is dried to yield compound iii.
In some preferred embodiments of the invention, the drying means comprises vacuum drying.
In some preferred embodiments of the present invention, the temperature of the drying is 70 to 100 ℃.
In some preferred embodiments of the present invention, the drying time is 24 to 48 hours.
In a second aspect of the invention, there is provided a modified benzisothiazolinone prepared by the method of the first aspect of the invention, wherein the modified benzisothiazolinone has a structural formula of
In a third aspect of the invention, an antibacterial material is provided, and raw materials for preparing the antibacterial material comprise the modified benzisothiazolinone of the second aspect of the invention.
According to the third aspect of the present invention, in some embodiments of the present invention, the raw materials for preparing the antibacterial material further include a resin and an antibacterial metal compound.
In some preferred embodiments of the invention, the modified benzisothiazolinone and resin are in a (100 to 120) mole ratio: (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antibacterial metal compound includes a compound containing Zn, ag, cu.
In some more preferred embodiments of the present invention, the antibacterial metal compound is a compound containing Ag.
In some preferred embodiments of the present invention, the antibacterial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of them.
In some preferred embodiments of the present invention, the resin comprises an eco-friendly acrylic resin.
In a fourth aspect of the invention, there is provided a method for preparing the antibacterial material according to the third aspect of the invention, the method comprising mixing a resin, an antibacterial metal compound and the modified benzisothiazolinone according to the second aspect of the invention.
The modified benzisothiazolinone after mixing is grafted onto the resin through hydroxyl, which can mention the antibacterial performance of the prepared material.
According to a fourth aspect of the invention, in some embodiments of the invention, the modified benzisothiazolinone and resin are in a (100 to 120) molar ratio: (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antibacterial metal compound includes a compound containing Zn, ag, and Cu.
In some more preferred embodiments of the present invention, the antibacterial metal compound is a compound containing Ag.
In some preferred embodiments of the present invention, the antibacterial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of them.
In some preferred embodiments of the present invention, the resin comprises an eco-friendly acrylic resin.
In some preferred embodiments of the present invention, the method for preparing the environmentally friendly acrylic resin comprises the following steps:
(1) Mixing methacrylate, acrylate, acrylic acid and an initiator to obtain a mixed solution;
(2) Dropwise adding the mixed solution obtained in the step (1) into a solvent for reaction, and drying after the reaction to obtain a solid resin;
(3) And (3) reacting the solid resin obtained in the step (2) with a pH regulator, and drying to obtain the environment-friendly acrylic material.
In some preferred embodiments of the present invention, the methacrylate in step (1) comprises any one of methyl methacrylate, ethyl methacrylate and butyl methacrylate.
In some preferred embodiments of the present invention, the acrylate in step (1) comprises any one of methyl acrylate, ethyl acrylate and butyl acrylate.
In some preferred embodiments of the present invention, the molar ratio of the methacrylate, the acrylate and the acrylic acid in step (1) is (70 to 80): (20-25): (5-10).
In some preferred embodiments of the present invention, the initiator comprises at least one of tetrabutyl titanate, dibenzoyl peroxide, azobisisobutyronitrile.
In some preferred embodiments of the present invention, the initiator is added in an amount of 1 to 3% by mass based on the total mass of the methacrylate, the acrylate and the acrylic acid.
In some preferred embodiments of the present invention, the solvent in step (2) comprises at least one of toluene, butyl acetate, xylene, n-butanol, isobutanol, propylene glycol butyl ether, and propylene glycol methyl ether.
In some preferred embodiments of the present invention, the reaction is carried out by adding the mixed solution dropwise to the solvent by heating under reflux in step (2).
In some preferred embodiments of the present invention, the temperature of the heating reflux is 80 ℃ to 100 ℃.
In some preferred embodiments of the present invention, the mixed solution is added dropwise within 2 to 5 hours.
In some preferred embodiments of the present invention, the time for the mixed solution to react in the solvent is 1h to 3h.
In some preferred embodiments of the present invention, the manner of drying in step (2) comprises vacuum drying.
In some preferred embodiments of the present invention, the temperature of the vacuum drying is 120 ℃ to 150 ℃.
In some preferred embodiments of the present invention, the vacuum drying time is 24 hours to 72 hours.
In some preferred embodiments of the present invention, the pH adjusting agent in step (3) comprises dimethylethanolamine.
In some preferred embodiments of the present invention, the reaction temperature in step (3) is 60 ℃ to 100 ℃.
In some preferred embodiments of the present invention, the drying in step (3) comprises vacuum drying.
In some preferred embodiments of the present invention, the drying temperature in step (3) is 60 to 80 ℃.
In some preferred embodiments of the present invention, the drying time in step (3) is 24 to 48 hours.
In some preferred embodiments of the present invention, the amount of the pH adjusting agent used in step (3) is 1 wt% to 2% by weight of the solid resin.
In some preferred embodiments of the present invention, in the preparation process of the environment-friendly acrylic resin, the modified benzisothiazolinone according to the second aspect of the present invention and the antibacterial metal compound are simultaneously added in step (3), and the antibacterial material is prepared after drying.
In some preferred embodiments of the invention, the molar ratio of the modified benzisothiazolinone to resin is (100 to 120): (50-80).
In some preferred embodiments of the present invention, the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
In some preferred embodiments of the present invention, the antibacterial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、 AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of them.
In a fifth aspect of the present invention, there is provided an application of the modified benzisothiazolinone of the second aspect of the present invention in preparing an antibacterial material.
According to a fifth aspect of the invention, in some embodiments of the invention, the antimicrobial material comprises an antimicrobial resin material.
In a sixth aspect of the present invention, there is provided a use of the antibacterial material according to the third aspect of the present invention in coating materials, inks, adhesives.
According to a sixth aspect of the invention, in some embodiments of the invention, the coating comprises an antifouling coating.
The invention has the beneficial effects that:
according to the invention, the modified benzisothiazolinone is grafted on the environment-friendly acrylic material, so that the obtained antibacterial environment-friendly acrylic material has a good antibacterial effect on staphylococcus aureus and escherichia coli, the antibacterial performance of the environment-friendly acrylic material is improved, and the material has an environment-friendly characteristic and has a good application prospect in the field of coatings.
Drawings
FIG. 1 is a statistical graph of the antibacterial ratio of the acrylic acid materials of examples 2 to 8 and comparative examples 1 to 2 against Staphylococcus aureus;
FIG. 2 is a statistical graph of the antibacterial ratio of the acrylic acid materials of examples 2 to 8 and comparative examples 1 to 2 against Escherichia coli.
Detailed Description
The present invention will be further described with reference to specific embodiments, and advantages and features of the present invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1 preparation of modified benzisothiazolinones
(1) The compound I
Adding potassium thiocyanate into a reaction kettle filled with N, N-Dimethylformamide (DMF), and adding catalyst CuI, cross-linking agent N, N' -dimethylethylenediamine (DMDAA) and organic base triethylammonium (Et) 3 N) in a molar ratio of compound I: potassium thiocyanate: and (2) CuI: DMEDA: et (Et) 3 N: DMF =5:10: 1:1:2:50, stirring the substances in DMF for 0.5h, then stirring and heating to 140 ℃ under the nitrogen atmosphere, and reacting for 48h at the temperature of 140 ℃. After the reaction is finished, cooling the mixture to 25 ℃, washing the mixture with distilled water to remove impurities, drying the mixture under the vacuum condition, wherein the drying temperature is 80 ℃, the drying time is 48 hours, and drying the mixture to obtain a compound II
(2) Adding NaOH into a compound II at 140 ℃ and 2000Pa for hydrolysis, wherein the molar ratio of NaOH to the compound II is 1:1, hydrolyzing for 5h, washing precipitated solid by absolute ethyl alcohol, drying the washed solid under the vacuum condition at the drying temperature of 80 ℃ for 48h to obtain a compound III
Example 2
(1) Adding 75mL of methyl methacrylate, 20mL of methyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of toluene into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 50g of modified benzisothiazolinone in example 1, 1g of ZnOH and 100g of solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and performing vacuum drying at 80 ℃ for 48 hours to obtain the antibacterial environment-friendly acrylic material.
Example 3
(1) Adding 75mL of methyl methacrylate, 15mL of butyl acrylate, 10mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of propylene glycol methyl ether into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 300mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 60g of modified benzisothiazolinone in example 1, 1g of ZnO and 100g of solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and performing vacuum drying at 80 ℃ for 48h to obtain the antibacterial environment-friendly acrylic material.
Example 4
(1) Adding 75mL of methyl methacrylate, 20mL of ethyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) 10mL of dimethylethanolamine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of ZnCl were added 2 And (3) heating 100g of the solid resin in the step (2) to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and drying in vacuum for 48 hours at 80 ℃ to obtain the antibacterial environment-friendly acrylic material.
Example 5
(1) Adding 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of toluene into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) 10mL of dimethyletherThe alcohol amine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of CuCl were added 2 And (3) heating 100g of the solid resin in the step (2) to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and drying in vacuum for 48 hours at 80 ℃ to obtain the antibacterial environment-friendly acrylic material.
Example 6
(1) Adding 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of toluene and xylene mixed solvent into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding the mixed solvent into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove the solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 70g of modified benzisothiazolinone in example 1, 1g of AgCl and 100g of solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and performing vacuum drying at 80 ℃ for 48 hours to obtain the antibacterial environment-friendly acrylic material.
Example 7
(1) Adding 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) 10mL of dimethylethanolamine was dissolved in 230mL of pure water, and 70g of the modified benzisothiazolinone of example 1 and 1g of Ag were added 2 And (3) heating 100g of the solid resin in the step (2) to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, finishing the reaction when no water is generated in the reaction, and drying in vacuum for 48 hours at 80 ℃ to obtain the antibacterial environment-friendly acrylic material.
Example 8
(1) Adding 75mL of methyl methacrylate, 20mL of butyl acrylate, 5mL of acrylic acid and 1g of dibenzoyl peroxide into a three-neck flask, and stirring and mixing for 1h to obtain a mixed solution;
(2) Adding 150mL of butyl acetate into a round-bottom flask, heating and refluxing at 80 ℃, dropwise adding into the mixed solution obtained in the step (1), completely dripping 150mL of toluene within 3h, reacting at 80 ℃ for 2h to obtain solvent type acrylic acid, and drying the solvent type acrylic acid under a vacuum condition to remove a solvent to obtain solid acrylic resin, wherein the drying temperature is 80 ℃, and the drying time is 48h;
(3) Dissolving 10mL of dimethylethanolamine in 230mL of pure water, adding 70g of modified benzisothiazolinone in example 1, 1g of AgOH and 100g of solid resin in the step (2), heating to 80 ℃ for reaction, heating to 120 ℃ for dehydration after the solution becomes clear and transparent, ending the reaction when no water is generated in the reaction, and vacuum-drying at 80 ℃ for 48 hours to obtain the antibacterial environment-friendly acrylic material.
Comparative example 1
The acrylic material of comparative example 1 was prepared by the same method as in example 6 except that the modified benzisothiazolinone and AgCl of example 1 were not added in step (3) in the preparation of the acrylic material of comparative example 1.
Comparative example 2
The acrylic material of comparative example 2 was prepared as in example 6 except that in the preparation of the acrylic material of comparative example 2, the modified benzisothiazolinone, which is a chemically pure reagent having a purity of 98%, purchased from an alatine reagent net, was replaced with an equal amount of commercially available benzisothiazolinone at step (3).
Test for antibacterial Properties
The antibacterial performance of the acrylic materials provided in the examples and comparative examples against staphylococcus aureus and escherichia coli was determined with reference to the GB/T31402-2015 standard.
The results of the antibacterial tests of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 on staphylococcus aureus and escherichia coli are shown in table 1 and fig. 1 to 2, fig. 1 is a statistical graph of the antibacterial rate of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 on staphylococcus aureus, and fig. 2 is a statistical graph of the antibacterial rate of the acrylic materials of examples 2 to 8 and comparative examples 1 to 2 on escherichia coli.
TABLE 1 results of antibacterial test on Staphylococcus aureus and Escherichia coli of acrylic materials in examples 2 to 8 and comparative examples 1 to 2
As can be seen from the data in table 1, the acrylic acid material prepared in the embodiment of the present invention has a high antibacterial rate against staphylococcus aureus and escherichia coli, which indicates that the addition of the modified benzisothiazolinone in embodiment 1 of the present invention improves the antibacterial performance of the acrylic acid material, and the larger the addition amount of the modified benzisothiazolinone, the better the antibacterial performance, and the highest antibacterial rate can reach 99.9%; comparative examples 4, 5 and 6 show that Ag + The antibacterial performance of the compound of the modified benzisothiazolinone is better.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of modified benzisothiazolinone is characterized by comprising the following steps:
reacting the compound I with potassium thiocyanate in a solvent to prepare a compound II, and hydrolyzing the compound II to prepare modified benzisothiazolinone shown in a formula III;
wherein the structural formula of the compound I is
X is selected from any one of F, cl, br and I;
wherein the structural formula of the compound II is
X is selected from any one of F, cl, br and I;
wherein the structural formula of the modified benzisothiazolinone of the formula III is
2. The modified benzisothiazolinone prepared by the process of claim 1, wherein the modified benzisothiazolinone has the formula
3. An antibacterial material, characterized in that the raw materials for preparing the antibacterial material comprise the modified benzisothiazolinone of claim 2.
4. The antibacterial material according to claim 3, wherein the raw materials for the preparation of the antibacterial material further comprise a resin and an antibacterial metal compound.
5. The method for preparing an antibacterial material according to claim 3 or 4, which comprises mixing a resin, an antibacterial metal compound and the modified benzisothiazolinone according to claim 2.
6. The method of claim 5 wherein the modified benzisothiazolinone and resin are in a molar ratio of (100 to 120): (50-80).
7. The method according to claim 5, wherein the antibacterial metal compound is added in an amount of 1 to 5% by mass of the resin.
8. The method as claimed in claim 5, wherein the antibacterial metal compound comprises ZnO, znCl 2 、ZnOH、Ag 2 O、AgCl、AgOH、CuO、CuCl 2 、Cu(OH) 2 Any one of them.
9. Use of a modified benzisothiazolinone according to claim 2 for the preparation of an antibacterial material.
10. Use of the antibacterial material according to claim 3 in paints, inks, adhesives.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101595880A (en) * | 2008-06-06 | 2009-12-09 | 比亚迪股份有限公司 | Complex antimicrobials and antimicrobial coating composition and antimicrobial coating material |
| CN104761667A (en) * | 2015-02-16 | 2015-07-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of zinc acrylate resin by grafting modified benzisothiazolinone |
| CN111635374A (en) * | 2019-09-28 | 2020-09-08 | 海南大学 | Structure and preparation method of acrylic resin containing benzisothiazolinone formamide functional monomer |
| CN113248666A (en) * | 2021-07-06 | 2021-08-13 | 山东科奥环境科技有限公司 | Efficient scale inhibition and dispersion agent for reverse osmosis membrane |
| CN113930117A (en) * | 2021-10-20 | 2022-01-14 | 广东美涂士建材股份有限公司 | Simple construction artistic coating and preparation method thereof |
-
2022
- 2022-07-12 CN CN202210813547.8A patent/CN115417828B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101595880A (en) * | 2008-06-06 | 2009-12-09 | 比亚迪股份有限公司 | Complex antimicrobials and antimicrobial coating composition and antimicrobial coating material |
| CN104761667A (en) * | 2015-02-16 | 2015-07-08 | 中国船舶重工集团公司第七二五研究所 | Method for preparation of zinc acrylate resin by grafting modified benzisothiazolinone |
| CN111635374A (en) * | 2019-09-28 | 2020-09-08 | 海南大学 | Structure and preparation method of acrylic resin containing benzisothiazolinone formamide functional monomer |
| CN113248666A (en) * | 2021-07-06 | 2021-08-13 | 山东科奥环境科技有限公司 | Efficient scale inhibition and dispersion agent for reverse osmosis membrane |
| CN113930117A (en) * | 2021-10-20 | 2022-01-14 | 广东美涂士建材股份有限公司 | Simple construction artistic coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| VIANI, FIORENZA ET AL.: "Synthesis and anti-bacterial activity of a library of 1,2-benzisothiazol-3(2H)-one (BIT) derivatives amenable of crosslinking to polysaccharides", 《TETRAHEDRON》, vol. 1997, no. 13, pages 127 - 128 * |
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