CN114044877A - N-halamine type antibacterial polyurethane material and preparation method and application thereof - Google Patents
N-halamine type antibacterial polyurethane material and preparation method and application thereof Download PDFInfo
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- CN114044877A CN114044877A CN202111358983.2A CN202111358983A CN114044877A CN 114044877 A CN114044877 A CN 114044877A CN 202111358983 A CN202111358983 A CN 202111358983A CN 114044877 A CN114044877 A CN 114044877A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 98
- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002313 adhesive film Substances 0.000 claims abstract description 12
- 239000004753 textile Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 27
- -1 nitrogen halide amine Chemical class 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 26
- 230000026030 halogenation Effects 0.000 claims description 18
- 238000005658 halogenation reaction Methods 0.000 claims description 18
- 239000002562 thickening agent Substances 0.000 claims description 17
- 239000002518 antifoaming agent Substances 0.000 claims description 15
- 239000004970 Chain extender Substances 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- 239000007844 bleaching agent Substances 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002357 guanidines Chemical class 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 13
- 239000004744 fabric Substances 0.000 abstract description 9
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- 230000008569 process Effects 0.000 abstract description 9
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- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 12
- 239000011527 polyurethane coating Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- KMSRVXJGTIRNNK-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen carbonate Chemical class NC(N)=N.OC(O)=O KMSRVXJGTIRNNK-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a nitrogen halamine type antibacterial polyurethane material, a preparation method and application thereof, and relates to the field of polyurethane compositions. The invention has simple synthesis process, can repeatedly chloridize to enhance the antibacterial property in practical application, and is beneficial to practical production and use; the adhesive film has high strength and excellent adhesive force; the chlorinated coating has good and lasting antibacterial performance and has great application prospect in the fields of antibacterial textile fabrics, toy coatings and medical appliances.
Description
Technical Field
The invention relates to the field of polyurethane compositions, in particular to a nitrogen halide amine type antibacterial polyurethane.
Background
Polyurethane (PU) has been widely used in the fields of children's toys, yoga mats, furniture, medical aerospace, military and the like due to its excellent physical and chemical properties such as good wear resistance, oil resistance, corrosion resistance, high flame retardancy and the like. Unfortunately, like most high molecular weight polymers, polyurethane materials are inevitably contaminated with microorganisms. Contact with infants can cause cross-contamination, cross-infection, or spread of bacterial diseases. Therefore, in recent years, research and development of antibacterial and environment-friendly materials are receiving more and more attention.
With the continuous research, different antibacterial substances are synthesized by different methods and introduced into polymer materials to achieve certain antibacterial effects.
Among the many potential antibacterial substances, the nitrogen halide amine type compound is an ideal material for preparing antibacterial materials due to its inherent economic advantages, long-term stability, high durability, reproducibility, and non-toxicity to humans and the environment. The nitrogen halide amine type compounds kill microorganisms by releasing strongly oxidized free halogen cations, interfering with cellular enzymatic activity and metabolic processes. Interestingly, once the oxidizing halogen is consumed, the nitrogen halamine type compounds are easily charged by soaking them in bleach. Based on their unique antibacterial properties, nitrogen halide amine type compounds have been widely used in the medical and health fields, particularly water treatment, food safety and textile materials.
Most of the preparation methods that have been reported are uneconomical and the products exhibit non-persistent, unstable and inefficient activities, among other problems. Some chemical surface modifications may even degrade the mechanical and thermodynamic properties of the polymer. Therefore, there is a challenge and necessity to develop a simple strategy for preparing antibacterial polyurethane polymers having excellent mechanical and thermodynamic properties.
Disclosure of Invention
The invention aims to provide a nitrogen halide amine type antibacterial polyurethane material, a preparation method and application thereof, and aims to solve the problems that nitrogen halide amine type compounds in the prior art are non-persistent, unstable and low in efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
a nitrogen halide amine type antibacterial polyurethane material has a chemical structural formula as follows:
the invention also provides a preparation method of the N-halamine type antibacterial polyurethane material, which comprises the following steps:
s1, adding 10-20 parts by weight of guanidine salt, 1-5 parts by weight of 2-acetylbutyrolactone, 4-11 parts by weight of triethylamine and 15-29 parts by weight of absolute ethyl alcohol into a reactor, stirring for 30-60 minutes, reacting for 24-48 hours at 70-80 ℃, cooling to room temperature, and washing with ethyl alcohol to obtain a nitrogen halamine precursor A, wherein the structural formula of the nitrogen halamine precursor A is as follows:
s2, adding 20-30 parts of polyol, 4-8 parts of diisocyanate and 5-12 parts of N, N-dimethylformamide into another reactor, adding 0.002-0.004 part of catalyst, and reacting at 75-85 ℃ for 2-4 h in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 18-26 parts of N, N-dimethylformamide, 0.4-1.0 part of chain extender and 0.1-0.6 part of azohalamine precursor A which is dried for 12-24 hours under the vacuum condition at 50 ℃ into the prefabricated material B prepared in the step S2, and then reacting for 4-5 hours at the temperature of 75-80 ℃ to prepare azohalamine type antibacterial polyurethane emulsion C;
s4, preparing the prepared emulsion C into an adhesive film at room temperature, and placing the adhesive film in a sodium hypochlorite solution with the concentration of 1% -5% or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Further, the guanidine salt in S1 is one or more of guanidine carbonate, guanidine hydrochloride and guanidine nitrate.
Further, the diisocyanate in S2 is an aromatic diisocyanate, a diphenylmethane diisocyanate or an aliphatic diisocyanate, and the catalyst is stannous octoate.
Further, the chain extender in S3 is one of 1, 4-butanediol BDO, 1, 6-hexanediol and diethylene glycol, and vacuum drying is further included to recover N, N-dimethylformamide after the reaction in S3 is finished.
Further, the halogenation time in S4 is 1-5 min.
Further, the adhesive film in S4 comprises, by weight, 0.1-0.25 part of a defoaming agent, 1.5-2 parts of a thickening agent and 75-106 parts of a nitrogen halide amine type antibacterial polyurethane emulsion C.
Further, the defoaming agent is an organic silicon defoaming agent.
Further, the thickener is an acrylate-type thickener.
The beneficial technical effects of the invention are as follows:
1. the weather resistance and the thermodynamic property of the polyurethane coating adhesive are improved by introducing a crosslinking system, and the nitrogen halamine precursor A is a structural formula which is easy to form an H bond, so that the stability of the adhesive film is improved, the crosslinking degree of the system can be increased, the firmness and the mechanical property of the polyurethane coating are improved, and the halogenation process is further simple and convenient. The material used for halogenation is low in price and easy to obtain, and the antibacterial coating has the performance of repeated halogenation regeneration and accords with the trend of green development. The antibacterial polyurethane material prepared from the nitrogen halamine precursor A is more in line with the green chemical development concept while improving the weather resistance and chemical resistance of a polyurethane coating adhesive film to a certain extent, and provides more possibilities for the research direction of the polyurethane coating adhesive.
2. The halogenation of the material can be realized by only adding a small amount of sodium hypochlorite with low concentration or a household bleaching agent, and the industrial application of the polyurethane coating is more facilitated.
3. According to the invention, the nitrogen halamine precursor A is introduced into the polyurethane prepolymer, so that the aims of long-term antibiosis and renewable antibiosis are achieved. The synthetic process is relatively simple, the antibacterial rate of the coating adhesive can reach 99.9%, and the nitrogen halamine has small cytotoxicity, long-lasting antibacterial property and can be repeatedly chloridized and regenerated, so the coating adhesive has good use value.
Drawings
FIG. 1 is a graph showing the antibacterial effect of a nitrogen-halogen amine type polyurethane coating adhesive film of a control group tested by a film pasting method (GB/T21866-2008);
FIG. 2 is a graph of the antibacterial effect of the test of embodiment 2 by using a sticking film method (GB/T21866-2008);
FIG. 3 is a graph of the antibacterial effect of the test of embodiment 3 by the application method (GB/T21866-2008);
FIG. 4 is a graph of the antibacterial effect of the test of embodiment 4 by the application method (GB/T21866-2008);
FIG. 5 is a graph showing the antibacterial effect of the test of example 5 by the application method (GB/T21866-2008);
FIG. 6 is a graph showing the antibacterial effect of example 6 tested by a membrane sticking method (GB/T21866-2008).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and the structural formula is as follows:
the invention also provides a preparation method of the N-halamine type antibacterial polyurethane material, which comprises the following steps:
s1, adding 10-20 parts by weight of guanidine salt, 1-5 parts by weight of 2-acetylbutyrolactone, 4-11 parts by weight of triethylamine and 15-29 parts by weight of absolute ethyl alcohol into a reactor, stirring for 30-60 minutes, reacting for 24-48 hours at 70-80 ℃, cooling to room temperature, and washing with ethyl alcohol to obtain a nitrogen halamine precursor A, wherein the structural formula of the nitrogen halamine precursor A is as follows:
s2, adding 20-30 parts of polyol, 4-8 parts of diisocyanate and 5-12 parts of N, N-dimethylformamide into another reactor, adding 0.002-0.004 part of catalyst, and reacting at 75-85 ℃ for 2-4 h in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 18-26 parts of N, N-dimethylformamide, 0.4-1.0 part of chain extender and 0.1-0.6 part of azohalamine precursor A which is dried for 12-24 hours under the vacuum condition at 50 ℃ into the prefabricated material B prepared in the step S2, and then reacting for 4-5 hours at the temperature of 75-80 ℃ to prepare azohalamine type antibacterial polyurethane emulsion C;
s4, preparing the prepared emulsion C into an adhesive film at room temperature, and placing the adhesive film in a sodium hypochlorite solution with the concentration of 1% -5% or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Wherein, the glue film in S4 can be a glue film prepared from the N-halamine type antibacterial polyurethane emulsion C alone, and the structural formula of the product obtained after the film is formed and halogenated alone is as follows:
in order to improve the quality and effect of the formed film, the glue film comprises 0.1-0.25 part by weight of defoaming agent, 1.5-2 parts by weight of thickening agent and 75-106 parts by weight of nitrogen halide amine type antibacterial polyurethane emulsion C, the obtained mixture is prepared into a film or coated on the upper surface of a fabric to form a film, and then halogenation is carried out, wherein the halogenated structural formula of the nitrogen halide amine type antibacterial polyurethane emulsion C in the mixture is shown as the formula (1); the selection of the invention is to add the defoaming agent and the thickening agent into the N-halamine type antibacterial polyurethane emulsion C.
Wherein the defoaming agent is an organic silicon defoaming agent, and the thickening agent is an acrylate thickening agent.
The following are specific preparation examples.
Example 1
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts of guanidine carbonate salt, 2 parts of 2-acetylbutyrolactone, 4 parts of triethylamine and 20 parts of absolute ethyl alcohol into a reactor according to parts by weight, stirring for 30 minutes, reacting at 78 ℃ for 24 hours, cooling to room temperature, and washing with ethanol to obtain a nitrogen haloamine precursor A;
s2, adding 20 parts of polyether N220, 5 parts of aliphatic diisocyanate IPDI and 7 parts of N, N-dimethylformamide DMF into another reactor, adding 0.002 part of catalyst into the reactor, and reacting for 2 hours at 80 ℃ in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 20 parts of N, N-dimethylformamide DMF (dimethyl formamide), O.8 parts of chain extender BDO and 0.15 part of nitrogen halide amine precursor A which is dried for 24 hours at 50 ℃ under the vacuum condition into the prefabricated material B prepared by S2, reacting for 4 hours at 78 ℃ to prepare nitrogen halide amine type antibacterial polyurethane emulsion C, and drying in vacuum after the reaction is finished to recover a solvent DMF; wherein the structural formula of the N-halamine type antibacterial polyurethane emulsion C is as follows:
s4, mixing 70 parts by weight of the N-halamine type antibacterial polyurethane emulsion C, 0.1 part of the organic silicon defoamer and 1.5 parts by weight of the acrylate type thickener, preparing a film at room temperature or coating the mixture on the surface of a fabric to form a film, and then placing the film in a sodium hypochlorite solution with the concentration of 1% or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 2
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts of guanidine carbonate salt, 2 parts of 2-acetylbutyrolactone, 4 parts of triethylamine and 20 parts of absolute ethyl alcohol into a reactor according to parts by weight, stirring for 30 minutes, reacting at 78 ℃ for 24 hours, cooling to room temperature, and washing with ethanol to obtain a nitrogen haloamine precursor A;
s2, adding 20 parts of polyether N220, 5 parts of aliphatic diisocyanate IPDI and 7 parts of N, N-dimethylformamide DMF into another reactor, adding 0.002 part of catalyst into the reactor, and reacting for 2 hours at 80 ℃ in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 20 parts of N, N-dimethylformamide DMF (dimethyl formamide), O.8 parts of chain extender BDO and 0.2 part of nitrogen halide amine precursor A which is dried for 24 hours at 50 ℃ under the vacuum condition into the prefabricated material B prepared by S2, reacting for 4 hours at 78 ℃ to prepare nitrogen halide amine type antibacterial polyurethane emulsion C, and drying in vacuum after the reaction is finished to recover a solvent DMF; wherein the structural formula of the N-halamine type antibacterial polyurethane emulsion C is as follows:
s4, mixing 75 parts by weight of N-halamine type antibacterial polyurethane emulsion C, 0.1 part of silicone defoaming agent and 1.5 parts by weight of acrylate type thickening agent, preparing a film at room temperature or coating the mixture on the surface of a fabric to form a film, and then placing the film in a 1% sodium hypochlorite solution or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 3
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts of guanidine carbonate salt, 3 parts of 2-acetylbutyrolactone, 4 parts of triethylamine and 20 parts of absolute ethyl alcohol into a reactor according to parts by weight, stirring for 30 minutes, reacting at 78 ℃ for 24 hours, cooling to room temperature, and washing with ethanol to obtain a nitrogen haloamine precursor A;
s2, adding 22 parts of polyether N220, 6 parts of aliphatic diisocyanate IPDI and 9 parts of N, N-dimethylformamide DMF into a reactor, adding 0.003 part of catalyst stannous octoate, and reacting at 80 ℃ for 2.5 hours in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 22 parts of N, N-dimethylformamide DMF, 0.7 part of chain extender BDO and 0.3 part of nitrogen halamine precursor A which is dried for 24 hours at the temperature of 50 ℃ under the vacuum condition into the prefabricated material B prepared by the step S2, and then continuously reacting for 4.5 hours at the temperature of 78 ℃ to prepare nitrogen halamine type antibacterial polyurethane emulsion C; after the reaction is finished, the solvent DMF is recovered by vacuum drying.
S4, mixing 80 parts by weight of the N-halamine type antibacterial polyurethane emulsion C, 0.15 part by weight of an organic silicon defoamer and 1.6 parts by weight of an acrylate type thickener, preparing a film at room temperature or coating the mixture on the surface of a fabric to form a film, and then placing the film in a sodium hypochlorite solution with the concentration of 1% or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 4
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts by weight of guanidine carbonate, 4 parts by weight of 2-acetylbutyrolactone, 4 parts by weight of triethylamine and 25 parts by weight of absolute ethyl alcohol into a reactor, stirring for 30 minutes, reacting at 78 ℃ for 24 hours, cooling to room temperature, and washing with ethyl alcohol to obtain a nitrogen haloamine precursor A;
s2, adding 24 parts of polyether N220, 6 parts of aliphatic diisocyanate IPDI and 9 parts of N, N-dimethylformamide DMF into a reactor, adding 0.003 part of catalyst, and reacting at 80 ℃ for 3 hours in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 25 parts of N, N-dimethylformamide DMF (dimethyl formamide), 0.6 part of chain extender BDO and 0.35 part of nitrogen halamine precursor A which is dried for 24 hours at the temperature of 50 ℃ under the vacuum condition into the prefabricated material B prepared by the step S2, and then continuously reacting for 4.5 hours at the temperature of 78 ℃ to prepare nitrogen halamine type antibacterial polyurethane emulsion C;
s4, mixing 85 parts by weight of N-halamine type antibacterial polyurethane emulsion C, 0.2 part by weight of silicone defoaming agent and 1.7 parts by weight of acrylate type thickening agent, preparing a film at room temperature or coating the mixture on the surface of a fabric to form a film, and then placing the film in a 1% sodium hypochlorite solution or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 5
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts of guanidine carbonate salt, 5 parts of 2-acetylbutyrolactone, 4 parts of triethylamine and 27 parts of absolute ethyl alcohol into a reactor according to parts by weight, stirring for 30 minutes, reacting at 78 ℃ for 30 hours, cooling to room temperature, washing with ethanol to obtain a nitrogen haloamine precursor A;
s2, adding 28 parts of polyether N220, 6 parts of aliphatic diisocyanate IPDI and 10 parts of N, N-dimethylformamide DMF into a reactor, adding 0.003 part of catalyst, and reacting at 80 ℃ for 3.5 hours in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 20 parts of N, N-dimethylformamide DMF, 0.5 part of chain extender BDO and 0.4 part of nitrogen halogen amine precursor A which is dried for 28 hours at the temperature of 50 ℃ under the vacuum condition into the prefabricated material B prepared by the S2, and then continuing to react for 5 hours at the temperature of 78 ℃ to prepare nitrogen halogen amine type antibacterial polyurethane emulsion C;
s4, mixing 95 parts by weight of N-halamine type antibacterial polyurethane emulsion C, 0.3 part by weight of silicone defoaming agent and 1.7 parts by weight of acrylate type thickening agent, preparing a film at room temperature or coating the mixture on the surface of a fabric to form a film, and then placing the film in a 1% sodium hypochlorite solution or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 6 (No antifoam and thickener added on the basis of example 3)
The embodiment provides a nitrogen halide amine type antibacterial polyurethane material which can be used in the fields of toy coatings, textile coatings, medical instruments and the like, and is prepared by adopting the following process:
s1, adding 10 parts of guanidine carbonate salt, 3 parts of 2-acetylbutyrolactone, 4 parts of triethylamine and 20 parts of absolute ethyl alcohol into a reactor according to parts by weight, stirring for 30 minutes, reacting at 78 ℃ for 24 hours, cooling to room temperature, and washing with ethanol to obtain a nitrogen haloamine precursor A;
s2, adding 22 parts of polyether N220, 6 parts of aliphatic diisocyanate IPDI and 9 parts of N, N-dimethylformamide DMF into a reactor, adding 0.003 part of catalyst stannous octoate, and reacting at 80 ℃ for 2.5 hours in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 22 parts of N, N-dimethylformamide DMF, 0.7 part of chain extender BDO and 0.3 part of nitrogen halamine precursor A which is dried for 24 hours at the temperature of 50 ℃ under the vacuum condition into the prefabricated material B prepared by the step S2, and then continuously reacting for 4.5 hours at the temperature of 78 ℃ to prepare nitrogen halamine type antibacterial polyurethane emulsion C; after the reaction is finished, the solvent DMF is recovered by vacuum drying.
S4, preparing 80 parts by weight of the N-halamine type antibacterial polyurethane emulsion C into a film at room temperature or coating the film on the surface of a fabric to form a film, and then placing the film into a 1% sodium hypochlorite solution or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
Example 7
Performance testing
The films prepared in examples 1-6 adopt a film pasting method, the antibacterial performance is tested according to GB/T21866-2008, the antibacterial rate data is shown in Table 1, and the antibacterial rate of example 1 is 76.4%; wherein, fig. 1 is a graph of the antibacterial effect of the control group (i.e. the product azohalamine type antibacterial polyurethane emulsion C obtained in S3 in example 2 is directly prepared into a film as the control group, and is not halogenated), and it can be seen from the graph that the control group does not have the antibacterial performance; the antibacterial effect chart of example 2 is shown in fig. 2, and compared with the control group shown in fig. 1, the antibacterial rate of the obtained N-halamine-type antibacterial polyurethane material to escherichia coli is 93.8%, which indicates that the N-halamine-type antibacterial polyurethane material obtained by the invention has good antibacterial performance; the antibacterial effect diagrams of examples 3-6 are shown in fig. 3-6, and compared with the control group shown in fig. 1, the antibacterial rate of the film obtained in examples 3-6 to escherichia coli is 99.9%, which shows that the film has excellent antibacterial performance, and the antibacterial performance of the antibacterial material is basically not affected by the defoaming agent and the thickening agent as shown in examples 6 and 6.
Examples 1-6 the products obtained by coating the surface of a fabric were tested for coating hydrostatic pressure according to GB/74744-1997; GB/T12704-1991 tests the moisture permeability of the coating; GB/T3920-1997 tests the coatings for dry crockfastness with the test data given in Table 1 below.
Nitrogen halide amine type antibacterial polyurethane coating film performance
TABLE 1
The film obtained by the invention has good and lasting antibacterial performance (the method is a long-term antibacterial method by bonding the nitrogen halamine precursor on the polyurethane framework through chemical reaction, the nitrogen halamine type precursor A plays a role similar to a chain extender, and the-N-H bond is converted into the-N-Cl bond through sodium hypochlorite halogenation, so that the purpose of long-term antibacterial is achieved), the washing fastness is high, the antibacterial performance is recovered through secondary halogenation, the operation is simple and convenient, and the like, and the invention has good application prospect in the field of antibacterial polyurethane coating glue.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A nitrogen halide amine type antibacterial polyurethane material has a chemical structural formula as follows:
2. the method for preparing the N-halamine-type antibacterial polyurethane material according to claim 1, comprising the steps of:
s1, adding 10-20 parts by weight of guanidine salt, 1-5 parts by weight of 2-acetylbutyrolactone, 4-11 parts by weight of triethylamine and 15-29 parts by weight of absolute ethyl alcohol into a reactor, stirring for 30-60 minutes, reacting for 24-48 hours at 70-80 ℃, cooling to room temperature, and washing with ethyl alcohol to obtain a nitrogen halamine precursor A, wherein the structure of the nitrogen halamine precursor A is as follows:
s2, adding 20-30 parts of polyol, 4-8 parts of diisocyanate and 5-12 parts of N, N-dimethylformamide into another reactor, adding 0.002-0.004 part of catalyst, and reacting at 75-85 ℃ for 2-4 h in a nitrogen atmosphere to obtain a prefabricated material B;
s3, adding 18-26 parts of N, N-dimethylformamide, 0.4-1.0 part of chain extender and 0.1-0.6 part of azohalamine precursor A which is dried for 12-24 hours under the vacuum condition at 50 ℃ into the prefabricated material B prepared in the step S2, and then reacting for 4-5 hours at the temperature of 75-80 ℃ to prepare azohalamine type antibacterial polyurethane emulsion C;
s4, preparing the prepared emulsion C into an adhesive film at room temperature, and placing the adhesive film in a sodium hypochlorite solution with the concentration of 1% -5% or a household bleaching agent for halogenation to obtain the N-halamine type antibacterial polyurethane material.
3. The method of claim 2, wherein the guanidine salt in S1 is one or more of guanidine carbonate, guanidine hydrochloride and guanidine nitrate.
4. The method for preparing N-halamine-type antibacterial polyurethane material according to claim 3, wherein the diisocyanate in S2 is aromatic diisocyanate, diphenylmethane diisocyanate or aliphatic diisocyanate, and the catalyst is stannous octoate.
5. The method for preparing N-halamine-type antibacterial polyurethane material according to claim 4, wherein the chain extender in S3 is one of 1, 4-butanediol, 1, 6-hexanediol, and diethylene glycol, and vacuum drying to recover N, N-dimethylformamide is further included after the reaction in S3 is completed.
6. The method for preparing N-halamine type antibacterial polyurethane material according to claim 5, wherein the halogenation time in S4 is 1-5 min.
7. The method for preparing N-halamine-type antibacterial polyurethane material according to claim 6, wherein the adhesive film in S4 comprises, by weight, 0.1-0.25 parts of an antifoaming agent, 1.5-2 parts of a thickener, and 75-106 parts of N-halamine-type antibacterial polyurethane emulsion C.
8. The method for producing a N-halamine-type antibacterial polyurethane material according to claim 7, wherein the defoaming agent is a silicone-based defoaming agent.
9. The method for preparing a N-halamine-type antibacterial polyurethane material according to claim 8, wherein the thickener is an acrylate-type thickener.
10. Use of a azohalamine-type antibacterial polyurethane material according to claim 1 in the field of toy coatings, textile coatings or medical devices.
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| CN117720704A (en) * | 2024-02-01 | 2024-03-19 | 浙江梅盛新材料有限公司 | Aqueous polyurethane emulsion and preparation method and application thereof |
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