CN107987578A - A kind of preparation method of the surface coating products with antifouling sterilizing function - Google Patents
A kind of preparation method of the surface coating products with antifouling sterilizing function Download PDFInfo
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- CN107987578A CN107987578A CN201711298822.2A CN201711298822A CN107987578A CN 107987578 A CN107987578 A CN 107987578A CN 201711298822 A CN201711298822 A CN 201711298822A CN 107987578 A CN107987578 A CN 107987578A
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- antifouling
- preparation
- sterilizing function
- surface coating
- coating products
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- 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
Abstract
The invention discloses a kind of preparation method of the surface coating products with antifouling sterilizing function, it is at room temperature, Dopamine hydrochloride, zwitterionic monomer, quaternary ammonium salt monomer, crosslinking agent and oxidant are dissolved in Tris buffer solutions successively, stir evenly, form mixed solution, then by substrate surface dipping wherein, 10 60min of ultrasonic disperse takes out, and is cleaned with deionized water, is obtained after drying at room temperature.The method of the present invention is easy to be quick and from the limitation of type of substrate, and coating stability is good, and applicability is wide, has a extensive future.
Description
Technical field
The present invention relates to a kind of preparation method of the surface coating products with antifouling sterilizing function, belong to organic and inorganic compound
Close technical field of function materials.
Background technology
It can assign host surface new function and property by surface modification, common having of surface modifying method
Learn grafting, physics is compound and physical chemistry Graft Method etc..Chemical graft process passes through modifying agent and the chemistry of host material main body
React and realize compound, reduce the intrinsic performance of host material to a certain extent, influence the mechanical strength and chemistry of base material
Stability；Premised on non-covalently bonded of the physics composite algorithm between host material and surface reforming layer is made a concerted effort, therebetween
Weaker with reference to power, the functionalization top layer of modified product is easily destroyed, and stability is poor, and service life is short.
Poly-dopamine modified lithium is to be adhered to the new and effective surface modification technology for inspiring and growing up by Mussels in recent years,
By small molecule dopamine and its derivative in the oxidation autohemagglutination on inert material surface, provided newly to prepare high-performance composite materials
Approach.From 2007 first report since, poly-dopamine surface be modified the fields such as biology, medicine, catalysis, water process by
To extensive concern.Dopaminergic realizes polymerization by the oxidation of itself, will not destroy the structure of host material, and can preferably tie
The advantages of closing multiple material；Dopamine can infiltrate most of inert materials, have good adaptability as modified monomer.This
Outside, poly-dopamine modified lithium coating contains a large amount of active groups, can carry out secondary surface modification.But poly-dopamine surface is modified and also deposits
Poor, the limitation in limitation, such as poly-dopamine modified lithium reaction time length, the stability in organic solvent or acid-base environment
The use scope of poly-dopamine coating.
Amphoteric ion polymer containing anion, cation group, can combine a large amount of free water molecules at the same time, form water
Change layer, can effectively inhibit bacteria and to stick with protein.Amphoteric ion polymer is introduced into material surface, material surface can be improved
Anti-pollution and self-purification function, the fields such as medical device, sensor, water process, water-oil separating all have wide application before
Scape, nevertheless, the preparation of amphoteric ion polymer face coat is still limited by the complexity and applicable base materials of preparation method
Limitation.The method that the preparation generally use surface grafting of amphoteric ion polymer face coat or surface are fixed.Surface connects
The coating surface that is acted on by chemical covalent bonds of branch amphoteric ion polymer brush is with good stability and uniformity, but
Requirement to base material is stringent, it is necessary to substrate surface progress activation modification, must also strictly control reaction condition, and chemical modification
Journey is cumbersome, manufacturing cycle is longer.Surface immutable laws are by Van der Waals force, hydrogen bond action or charge effect by polymer with physics
The effect of non-covalent bond is fixed on substrate surface, simple compared with chemical graft process, quick, but needs premature polymerization thing and base material to carry out
The modification of electric charge or active group, is limited the scope of application of base material, and the combination power of polymer and base material is weak, face coat is steady
Qualitative difference, is unfavorable for long-time service.Therefore, the simplification of the stability of chemical action and physical action is combined,
Develop a kind of easy, quick, stabilization and from the preparation method of base material limitation, amphoteric ion polymer face coat is pushed away
Wide application is of great significance.
Preparing the common method of antibacterial surface coating includes nonactive antisepsis and active antibacterial method.Nonactive antisepsis is
By the modification of anti-adhesion substances in material surface, suppress initial bacteria and stick, formed using amphoteric ion polymer in material surface
Hydrated sheath can inhibit bacteria accumulation on surface.But the method is there is also shortcoming, once a small number of bacteriums are attached to anti-stick
Behind subordinate list face, the possibility to form biomembrane is still suffered from.Active antibacterial method is antiseptic to be added in material body or in material table
Antiseptic is fixed in face, the bacterium on surface is killed by antiseptic, so as to prevent the formation of biomembrane.Quaternary ammonium salt has good kill
Bacterium performance, its mechanism of action are mainly that cation passes through electrostatic force, hydrogen bond force and surfactant molecule and protein molecule
Between the effect such as hydrophobic binding, adsorb electronegative bacterial body, be gathered on cell membrane, generating chamber's inhibition effect, causes bacterium to give birth to
Length is suppressed and dead；Its hydrophobic alkyl can also be acted on the hydrophilic group of bacterium at the same time, change the permeability of film, lysis then occurs
Effect, destroys eucaryotic cell structure, causes the dissolving and death of cell.Amphoteric ion polymer and QAS polymer are introduced into base material
Surface is expected to form the face coat with good anti-pollution bactericidal effect.
The Chinese patent of the Publication No. CN105498291A reported at present discloses a kind of oil with self-purification function
Moisture off-network film and preparation method thereof, using stainless (steel) wire, aluminium alloy net or copper mesh as substrate, in coming to the surface for net surface and mesh
Learn acrylic polymer of the grafting containing amphiprotic group.The Chinese patent of Publication No. CN106422421A discloses a kind of filter
Paper is modified the method for preparing water-oil separationg film and application, using common qualitative filter paper as base material, by the adhesion of poly-dopamine,
In its surface structure PDA mediation layers, then the polyethylene glycol with active ester group or amphoteric ion polymer are situated between with PDA
The amino on conducting shell surface is fixed on surface by amidation covalence graft.The Chinese patent of Publication No. CN103394295A
A kind of hydrophilic PVDF composite filter membrane and preparation method thereof is disclosed, is produced by PVDF, DOPA analog assistant and the reaction of end ring oxygen PEO
Thing blending is prepared.The coating material that method made above obtains has good antifouling self-purification capacity, but does not possess and kill
Bacterium ability, and there are the problems such as complex process, complex steps, be further improved and optimize.
The content of the invention
In view of the deficiencies of the prior art, the problem to be solved in the present invention is to provide a kind of surface with antifouling sterilizing function
The preparation method of coating product.
The preparation method of surface coating products of the present invention with antifouling sterilizing function, step are：
(1) at room temperature, by Dopamine hydrochloride, zwitterionic monomer, quaternary ammonium salt monomer, crosslinking agent and oxidant in molar ratio
For 1:10~100:10~100:1~10:1~10 ratio, is dissolved in the Tris buffer solutions of pH=8.5 successively, and stirring is equal
It is even, form mixed solution；
(2) substrate surface is impregnated in mixed solution made from step (1), 10~60min of ultrasonic disperse takes out, and spends
Ionized water cleaning, drying at room temperature, that is, obtain the surface coating products with antifouling self-purification function.
In the preparation method of the above-mentioned surface coating products with antifouling self-purification function, the Dopamine hydrochloride, both sexes from
Sub- monomer, quaternary ammonium salt monomer, the molar ratio of crosslinking agent and oxidant are preferably 1:15~70:15~50:1~7:1~7.
Wherein, the molar ratio of the Dopamine hydrochloride, zwitterionic monomer, sterilization monomer, crosslinking agent and oxidant is optimal
Select 1:15~30:15~20:2~5:2~5.
In the preparation method of the above-mentioned surface coating products with antifouling sterilizing function, the zwitterionic monomer is preferred
2- methylacryoyloxyethyls phosphocholine, 2- methylacryoyloxyethyls sulphonic acid betaine or 2- methylacryoyloxyethyl carboxylics
Base glycine betaine.
In the preparation method of the above-mentioned surface coating products with antifouling sterilizing function, the quaternary ammonium salt monomer preferably third
Alkene acyloxyethyl trimethyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl ammonium bromide
Or methylacryoyloxyethyl trimethylammonium bromide.
In the preparation method of the above-mentioned surface coating products with antifouling sterilizing function, the preferred diamines of the crosslinking agent,
Polyamine or glutaraldehyde, or its several any mol ratio combination.
Wherein, the crosslinking agent most preferably diamines or glutaraldehyde.
In the preparation method of the above-mentioned surface coating products with antifouling sterilizing function, the preferred persulfuric acid of the oxidant
Salt, perchlorate, periodate or hydrogen peroxide.
Wherein, the oxidant most preferably potassium peroxydisulfate or ammonium persulfate.
In the preparation method of the above-mentioned surface coating products with antifouling sterilizing function, the base material for filter paper, sponge,
Cotton, polyvinylidene fluoride film, glass or metallic sieve.
Compared with prior art, the invention has the advantages that：
(1) method is easy to operate, it is only necessary to which poly-dopamine, amphoteric ion polymer and season can be achieved in step solution dipping
Ammonium salt monomer and from the limitation of type of substrate, effectively overcomes that existing method is complicated, table in the fixation of substrate surface
The problems such as face stability is poor, efficient, quick preparation method is provided for the face coat with antifouling sterilizing function.
(2) for dopamine while auto polymerization is aoxidized, its activity functional groups can trigger zwitterionic monomer, quaternary ammonium salt
The polymerization of monomer, the presence of oxidant accelerate polymerization speed.Rolled into a ball and reacted by the active function in crosslinking agent and poly-dopamine,
The oligomeric dopamine of soluble small molecule is cross-linked into 3 D stereo network structure, improves poly-dopamine, amphoteric ion polymer, season
Between ammonium salt polymer molecule and between poly-dopamine, amphoteric ion polymer molecule, QAS polymer and host material
Bond strength.
(3) preparation process condition is gentle, can carry out at normal temperatures, be easy to industrialization.
Embodiment
Below by the specific embodiment provided, the present invention is further explained, but following embodiments are served only for understanding the present invention
It is not limiting the scope of the present invention.
Embodiment 1：
(1) at room temperature, by Dopamine hydrochloride (38mg, 0.2mmol), 2- methylacryoyloxyethyl phosphocholines
(0.885g, 3mmol), acrylyl oxy-ethyl-trimethyl salmiac (0.581g, 3mmol), ethylenediamine (0.06g, 1mmol) and mistake
Ammonium sulfate (0.27g, 1mmol) is dissolved in Tris buffer solutions (20mL, 50mM, pH=8.5) successively, is stirred evenly, and is formed mixed
Close solution；
(2) ordinary filter paper is impregnated in the mixed solution that step (1) obtains, ultrasonic disperse 45min takes out, and uses deionization
Water cleaning, drying at room temperature, that is, obtain having the surface of antifouling sterilizing function to be modified filter paper.
Embodiment 2：
The present embodiment prepares face coat according to the identical mode of embodiment 1, differs only in step (2) with thin layer sea
Silk floss substitutes ordinary filter paper, obtains the surface modified sponge with antifouling sterilizing function.
Embodiment 3：
The present embodiment prepares face coat according to the identical mode of embodiment 1, differs only in step (2) with sheet glass
Ordinary filter paper is substituted, obtains the surface modified glass piece with antifouling sterilizing function.
Embodiment 4：
The present embodiment prepares face coat according to the identical mode of embodiment 1, differs only in step (2) with stainless steel
Sieve substitutes ordinary filter paper, obtains the surface modified stainless steel sieve with antifouling sterilizing function.
Embodiment 5：
(1) at room temperature, by Dopamine hydrochloride (38mg, 0.2mmol), 2- methylacryoyloxyethyl sulphonic acid betaines
(0.837g, 3mmol), acrylyl oxy-ethyl-trimethyl salmiac (0.581g, 3mmol), glutaraldehyde (0.10g, 1mmol) and mistake
Potassium sulfate (0.27g, 1mmol) is dissolved in Tris buffer solutions (20mL, 50mM, pH=8.5) successively, is stirred evenly, and is formed mixed
Close solution；
(2) ordinary filter paper is impregnated in the mixed solution that step (1) obtains, ultrasonic disperse 30min takes out, and uses deionization
Water cleaning, drying at room temperature, that is, obtain having the surface of antifouling sterilizing function to be modified filter paper.
Embodiment 6：
The present embodiment prepares face coat according to the identical mode of embodiment 5, differs only in step (2) with thin layer sea
Silk floss substitutes ordinary filter paper, obtains the surface modified sponge with antifouling sterilizing function.
Embodiment 7：
The present embodiment prepares face coat according to the identical mode of embodiment 5, differs only in step (2) with sheet glass
Ordinary filter paper is substituted, obtains the surface modified glass piece with antifouling sterilizing function.
Embodiment 8：
The present embodiment prepares face coat according to the identical mode of embodiment 5, differs only in step (2) with stainless steel
Sieve substitutes ordinary filter paper, obtains the surface modified stainless steel sieve with antifouling sterilizing function.
Embodiment 9：
(1) at room temperature, by Dopamine hydrochloride (57mg, 0.3mmol), 2- methylacryoyloxyethyl carboxybetaines
(0.972g, 4mmol), MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (0.622g, 3mmol) glutaraldehyde (0.15g,
1.5mmol) it is dissolved in Tris buffer solutions (20mL, 50mM, pH=8.5), stirs successively with potassium peroxydisulfate (0.81g, 3mmol)
Uniformly, mixed solution is formed；
(2) ordinary filter paper is impregnated in the mixed solution that step (1) obtains, ultrasonic disperse 15min takes out, and uses deionization
Water cleaning, drying at room temperature, that is, obtain having the surface of antifouling sterilizing function to be modified filter paper.
Embodiment 10：
The present embodiment prepares face coat according to the identical mode of embodiment 9, differs only in step (2) with thin layer sea
Silk floss substitutes ordinary filter paper, obtains the surface modified sponge with antifouling sterilizing function.
Embodiment 11：
The present embodiment prepares Thermo-sensitive face coat according to the identical mode of embodiment 9, differ only in step (2) with
Sheet glass substitutes ordinary filter paper, obtains the surface modified glass piece with antifouling sterilizing function.
Embodiment 12：
The present embodiment prepares Thermo-sensitive face coat according to the identical mode of embodiment 9, differ only in step (2) with
Stainless steel mesh substitutes ordinary filter paper, obtains the surface modified stainless steel sieve with antifouling sterilizing function.
Claims (10)
1. a kind of preparation method of the surface coating products with antifouling sterilizing function, step are：
(1) at room temperature, it is 1 in molar ratio by Dopamine hydrochloride, zwitterionic monomer, quaternary ammonium salt monomer, crosslinking agent and oxidant:
10~100:10~100:1~10:1~10 ratio, is dissolved in the Tris buffer solutions of pH=8.5, stirs evenly successively, shape
Into mixed solution；
(2) substrate surface is impregnated in mixed solution made from step (1), 10~60min of ultrasonic disperse takes out, and uses deionization
Water cleaning, drying at room temperature, that is, obtain the surface coating products with antifouling sterilizing function.
2. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that institute
The molar ratio for stating Dopamine hydrochloride, zwitterionic monomer, quaternary ammonium salt monomer, crosslinking agent and oxidant is 1:15~70:15~50:
1~7:1~7.
3. the preparation method according to claim 2 based on the surface coating products with antifouling sterilizing function, its feature exist
In the molar ratio of, the Dopamine hydrochloride, zwitterionic monomer, quaternary ammonium salt monomer, crosslinking agent and oxidant be 1:15~30:15
~20:2~5:2~5.
4. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that institute
The zwitterionic monomer stated is 2- methylacryoyloxyethyls phosphocholine, 2- methylacryoyloxyethyls sulphonic acid betaine or 2-
Methylacryoyloxyethyl carboxybetaine.
5. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that institute
The quaternary ammonium salt monomer stated is acrylyl oxy-ethyl-trimethyl salmiac, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acryloyl
Oxy-ethyl-trimethyl ammonium bromide or methylacryoyloxyethyl trimethylammonium bromide.
6. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that institute
The crosslinking agent stated is diamines, polyamine or glutaraldehyde, or its several any mol ratio combination.
7. the preparation method of the surface coating products with antifouling sterilizing function according to claim 5, it is characterised in that institute
The crosslinking agent stated is diamines or glutaraldehyde.
8. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that institute
The oxidant stated is persulfate, perchlorate, periodate or hydrogen peroxide.
9. the preparation method of the surface coating products with antifouling sterilizing function according to claim 8, it is characterised in that institute
The oxidant stated is potassium peroxydisulfate or ammonium persulfate.
10. the preparation method of the surface coating products with antifouling sterilizing function according to claim 1, it is characterised in that
The base material is filter paper, sponge, cotton, polyvinylidene fluoride film, glass or metallic sieve.
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| CN108586795A (en) * | 2018-05-09 | 2018-09-28 | 天津工业大学 | A kind of fast preparation method of super-hydrophobic three-dimensional sponge and its water-oil separating application |
| CN108815882A (en) * | 2018-06-15 | 2018-11-16 | 山东交通学院 | A kind of bionical water-oil separating material and preparation method thereof with antifouling sterilization and Dye Adsorption function |
| CN108822326A (en) * | 2018-06-08 | 2018-11-16 | 西北大学 | A kind of amphoteric ion copolymer, preparation method and the method for constructing coating using it |
| CN110642980A (en) * | 2018-06-27 | 2020-01-03 | 华东理工大学 | Ultrahigh-strength mineralized hydrogel, and synthesis method and application thereof |
| CN112064348A (en) * | 2020-08-31 | 2020-12-11 | 中国科学院地球环境研究所 | Sterilizing antifouling melt-blown fabric and processing technology thereof |
| CN112295022A (en) * | 2020-10-11 | 2021-02-02 | 北京科技大学 | Dopamine-zwitterion antibacterial coating and preparation method thereof |
| CN112341851A (en) * | 2020-10-28 | 2021-02-09 | 徐晨 | Mixed charge polymer coating and method of polymer coating |
| CN114163554A (en) * | 2021-07-28 | 2022-03-11 | 南方医科大学珠江医院 | One-step method for preparing polydopamine-zwitterionic polymer copper-containing antibacterial coating and application thereof |
| CN114456308A (en) * | 2022-02-28 | 2022-05-10 | 华中科技大学 | Photo-thermal hydrogel, preparation method and application thereof, and photo-thermal conversion evaporator |
| CN114456437A (en) * | 2022-01-26 | 2022-05-10 | 武汉理工大学 | Polydopamine coating modified antibacterial polyurethane dressing and preparation method and application thereof |
| CN114474957A (en) * | 2021-12-31 | 2022-05-13 | 漳州香洲皮革有限公司 | Method for manufacturing bright spot leopard line double-color leather |
| CN115926507A (en) * | 2022-11-14 | 2023-04-07 | 苏州大学 | Amphoteric ion coating with adjustable ions, co-deposition one-step preparation method and application thereof |
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| CN108586795A (en) * | 2018-05-09 | 2018-09-28 | 天津工业大学 | A kind of fast preparation method of super-hydrophobic three-dimensional sponge and its water-oil separating application |
| CN108822326B (en) * | 2018-06-08 | 2021-06-04 | 西北大学 | Zwitterionic copolymer, preparation method and method for constructing coating by utilizing zwitterionic copolymer |
| CN108822326A (en) * | 2018-06-08 | 2018-11-16 | 西北大学 | A kind of amphoteric ion copolymer, preparation method and the method for constructing coating using it |
| CN108815882A (en) * | 2018-06-15 | 2018-11-16 | 山东交通学院 | A kind of bionical water-oil separating material and preparation method thereof with antifouling sterilization and Dye Adsorption function |
| CN108815882B (en) * | 2018-06-15 | 2020-05-29 | 山东交通学院 | Bionic oil-water separation material with antifouling, sterilizing and dye adsorption functions and preparation method thereof |
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| CN112064348B (en) * | 2020-08-31 | 2022-03-11 | 中国科学院地球环境研究所 | Sterilizing antifouling melt-blown fabric and processing technology thereof |
| CN112064348A (en) * | 2020-08-31 | 2020-12-11 | 中国科学院地球环境研究所 | Sterilizing antifouling melt-blown fabric and processing technology thereof |
| CN112295022A (en) * | 2020-10-11 | 2021-02-02 | 北京科技大学 | Dopamine-zwitterion antibacterial coating and preparation method thereof |
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| CN114456437A (en) * | 2022-01-26 | 2022-05-10 | 武汉理工大学 | Polydopamine coating modified antibacterial polyurethane dressing and preparation method and application thereof |
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Application publication date: 20180504 |