CN113402971A - Glass bead filled silicone gel anti-fouling bacteriostatic coating and preparation method and application thereof - Google Patents
Glass bead filled silicone gel anti-fouling bacteriostatic coating and preparation method and application thereof Download PDFInfo
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
Abstract
The invention discloses a preparation method of a silicone gel anti-fouling bacteriostatic coating filled with glass beads, which comprises the following steps: (1) mixing a quaternary ammonium salt monomer containing reactive double bonds, a hydrophilic monomer, a mercapto silane coupling agent and an organic solvent A, and initiating by an initiator under an inert atmosphere to prepare a quaternary ammonium salt hydrophilic polymer; (2) and (2) blending the quaternary ammonium salt hydrophilic polymer prepared in the step (1), polysiloxane, a catalyst, glass beads, a cross-linking agent which can be selectively added and an organic solvent B, and coating and curing to obtain the silicone gel anti-fouling and antibacterial coating filled with the glass beads. The coating prepared by the invention has excellent antibacterial property, protein adsorption resistance and higher mechanical strength, and is suitable for the fields of marine antifouling, biomedical treatment and the like.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a silicone gel anti-fouling and antibacterial coating filled with glass beads, a preparation method of the silicone gel anti-fouling and antibacterial coating, and application of the silicone gel anti-fouling and antibacterial coating in the fields of marine antifouling and biomedical science.
Background
The organosilicon material has the advantages of high biocompatibility, low surface energy, no toxicity, no odor, good physiological inertia and the like, and is widely applied to the fields of marine antifouling, biomedical, textile, agriculture, building, food packaging and the like. However, the surface of the organosilicon material is easy to grow and propagate various harmful microorganisms to cause surface pollution, so that various problems are brought to practical application, and in order to solve the problems of surface bacterial pollution and the like when the organosilicon material is applied in the fields of biological medical treatment, marine antifouling and the like, the organosilicon material needs to be subjected to antifouling modification to obtain the organosilicon antifouling paint with antibacterial and antifouling properties.
Water has strong hydrogen bond binding capacity, and the hydrophilic material can react with water molecules to form hydrogen bonds, so that a hydration layer is formed on the surface of the material, thereby effectively resisting the attachment of proteins, algae, bacteria and the like on the surface of the material and achieving a better anti-fouling effect.
For example, Chinese patent document with application publication No. CN 106634275A discloses a super-hydrophilic/underwater super-oleophobic coating material and a preparation method and application thereof; further, for example, chinese patent publication No. CN107936831A discloses a hydrophilic modified fouling release type marine antifouling paint and a preparation method thereof; for another example, chinese patent publication No. CN 111592781 a discloses a super-hydrophilic functional coating, and a preparation method and an application thereof.
The coating after hydrophilic modification can resist the attachment of fouling and improve the antifouling effect of the coating. However, the hydrated layer formed on the surface of the coating layer after hydrophilic modification alone cannot prevent the adhesion of all the stains, and once the stains are attached, the coating cannot prevent the stains from propagating on the surface of the coating layer, thereby causing larger stains.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a silicone gel anti-fouling bacteriostatic coating filled with glass beads, and the prepared coating has excellent antibacterial performance, protein adsorption resistance and higher mechanical strength and is suitable for the fields of marine antifouling, biomedical treatment and the like.
The specific technical scheme is as follows:
a preparation method of a silicone gel anti-fouling bacteriostatic coating filled with glass beads comprises the following steps:
(1) mixing a quaternary ammonium salt monomer containing reactive double bonds, a hydrophilic monomer, a mercapto silane coupling agent and an organic solvent A, and initiating by an initiator under an inert atmosphere to prepare a quaternary ammonium salt hydrophilic polymer;
the quaternary ammonium salt monomer containing reactive double bonds is selected from one or more of methacryloyloxyethyl benzyl dimethyl ammonium chloride, methacryloyloxyethyl n-dodecyl dimethyl ammonium bromide, methacryloyloxyethyl n-hexadecyl dimethyl ammonium bromide, acryloyloxyethyl benzyl dimethyl ammonium chloride, acryloyloxyethyl n-dodecyl dimethyl ammonium bromide and acryloyloxyethyl n-hexadecyl dimethyl ammonium bromide;
the structural formulas of the hydrophilic monomers are respectively shown in the following formulas (I-1) to (I-6):
wherein x and y are independently selected from 3 to 25;
(2) and (2) blending the quaternary ammonium salt hydrophilic polymer prepared in the step (1), polysiloxane, a catalyst, glass beads, a cross-linking agent which can be selectively added and an organic solvent B, and coating and curing to obtain the silicone gel anti-fouling and antibacterial coating filled with the glass beads.
The invention discloses a preparation method of a silicone gel anti-fouling bacteriostatic coating filled with glass beads. Cations in the quaternary ammonium salt groups can be adsorbed on the surface of bacteria, and quaternary ammonium salt chain segments permeate into cell membranes to influence the mobility of phospholipid bilayers in the cell membranes, interfere the interaction between membrane proteins and lipids, and change the asymmetry of lipid arrangement, so that the cell membranes are damaged, substances in the bacteria leak, and the sterilization effect is achieved. The hydrophilic groups can react with water molecules to form hydrogen bonds, and a hydration layer is formed on the surface, so that the adhesion of proteins, algae, bacteria and the like on the surface is effectively resisted, and a better hydrophilic anti-fouling effect is achieved. The glass beads added as the filler improve the mechanical strength of the coating and simultaneously further enhance the hydrophilicity of the coating.
In the step (1):
the mercapto silane coupling agent is selected from one or more of mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane; mercaptopropyltrimethoxysilane is preferred.
The organic solvent A is selected from one or more of dichloromethane, dichloroethane, trifluoroethanol and trifluorobutanol; experiments show that in the preparation process in the step (1), the selection of the solvent is more critical, and if the solvent is not properly selected, if acetonitrile is selected as the solvent, the reaction can be continued due to the occurrence of a gelling phenomenon in the reactor after the reaction is carried out for a period of time, and the quaternary ammonium salt hydrophilic polymer can not be precipitated after the gelling phenomenon occurs.
The molar ratio of the quaternary ammonium salt monomer containing the reactive double bond to the hydrophilic monomer is 0.05-5: 1; preferably 0.5-3: 1.
the using amount of the mercapto silane coupling agent is 1-50% of the total molar amount of the monomers; preferably 10 to 30%.
The total mole amount of the monomers refers to the sum of the mole numbers of the quaternary ammonium salt monomer containing the reactive double bond and the hydrophilic monomer.
The dosage of the organic solvent A is 1-5 times of the total weight of the reactants; preferably 1 to 3 times.
The total weight of the reactants is the sum of the weights of all raw materials except the organic solvent A, namely the sum of the weights of the mercapto silane coupling agent, the quaternary ammonium salt monomer containing the reactive double bond and the hydrophilic monomer.
The initiator is selected from one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisobutyronitrile, azobiscyclohexyl and azobisisobutyric acid;
the adding mass of the initiator is 0.1-5.0% of the total weight of the monomers.
In the step (2):
the polysiloxane is selected from polydimethylsiloxane or hydroxymethyl-terminated polydimethylsiloxane, and the dynamic viscosity is 500-100000 mPa & s.
The catalyst is selected from an organic bismuth catalyst or an organic tin catalyst;
the organic bismuth catalyst is selected from one or more of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate; the organic tin catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate and dibutyltin maleate.
Preferably, the catalyst is selected from more environmentally friendly organic bismuth based catalysts.
The cross-linking agent is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate;
the organic solvent B is selected from one or more of trifluoroethanol, trifluorobutanol, xylene, toluene, dichloromethane, methane and acetonitrile.
Preferably:
the weight ratio of the quaternary ammonium salt hydrophilic polymer to the polysiloxane is 1-30: 100, respectively; more preferably 10 to 20: 100.
the mass of the glass beads is 1-20% of the total weight of the polymer;
the total weight of the polymer refers to the sum of the weight of the quaternary ammonium hydrophilic polymer and the weight of the polysiloxane.
The mass of the selectively added cross-linking agent is 1-15% of the total weight of the polymer;
the mass of the catalyst is 0.05-5.00% of the total weight of the polymer;
the dosage of the organic solvent B is 1-5 times of the total weight of the reactants.
In the step (2), the total weight of the reactants is the sum of the weights of all raw materials except the organic solvent B, namely the sum of the weights of the quaternary ammonium salt hydrophilic polymer, the polysiloxane, the catalyst, the glass beads and the optional crosslinking agent.
The curing temperature is room temperature.
The antibacterial performance of the coating prepared by the method is determined by the mutual cooperation and combined action of the quaternary ammonium salt monomer containing reactive double bonds, the hydrophilic monomer and the glass beads, and the hydrophilic anti-fouling performance of the coating is determined by the mutual cooperation and combined action of the hydrophilic monomer and the glass beads.
Preferably:
the hydrophilic monomer is selected from the following formulas (I-3) to (I-6) and is named as methacrylic acid sulfobetaine, acrylic acid sulfobetaine, methacryloyloxyethyl phosphorylcholine and acryloyloxyethyl phosphorylcholine in sequence;
the quaternary ammonium salt monomer containing reactive double bonds is selected from one or more of methacryloyloxyethyl n-dodecyl dimethyl ammonium bromide, methacryloyloxyethyl n-hexadecyl dimethyl ammonium bromide, acryloyloxyethyl n-dodecyl dimethyl ammonium bromide and acryloyloxyethyl n-hexadecyl dimethyl ammonium bromide;
the mass of the glass beads is 10-20% of the total weight of the polymer;
experiments show that the coating finally prepared by adopting the preferred quaternary ammonium salt monomer containing the reactive double bond, the hydrophilic monomer and the glass beads with the preferred content as raw materials has higher bacteriostatic effect and lower protein adsorption capacity.
Further preferably:
the hydrophilic monomer is selected from the formulas (I-5) to (I-6), namely, methacryloxyethyl phosphorylcholine and/or acryloxyethyl phosphorylcholine;
the quaternary ammonium salt monomer containing reactive double bonds is selected from methacryloyloxyethyl n-hexadecyl dimethyl ammonium bromide and/or acryloyloxyethyl n-hexadecyl dimethyl ammonium bromide;
the mass of the glass beads is 15-20% of the total weight of the polymer.
Tests show that the finally prepared coating has higher bacteriostatic effect and lower protein adsorption capacity by adopting the more preferable quaternary ammonium salt monomer containing reactive double bonds, the hydrophilic monomer and the more preferable content of glass beads as raw materials.
The invention also discloses a silicone gel anti-fouling and antibacterial coating filled with the glass beads, which has stronger bactericidal property and anti-protein adsorbability and better mechanical property, and is particularly suitable for application in the fields of marine antifouling and biomedical.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method disclosed by the invention, the quaternary ammonium salt group and the hydrophilic group are introduced into the polysiloxane coating, the glass beads are further filled, and the polysiloxane coating is modified by utilizing the mutual cooperation of the quaternary ammonium salt group, the hydrophilic group and the glass beads, so that the coating can obtain excellent antibacterial and bactericidal performance, antifouling performance and mechanical performance. The coating also has the advantages of fast film forming, good weather resistance, chemical reagent resistance and wear resistance, etc.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents also fall within the scope of the invention defined by the claims.
Example 1
(1) Adding 0.78g (0.004mol) of 3-mercaptopropyltrimethoxysilane, 4.18g (0.015mol) of methacryloyloxyethylbenzyldimethylammonium chloride, 3.25g (0.008mol) of polyethylene glycol monomethyl ether-methacrylate and 20g of dichloromethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting for 12h at 80 ℃ in a nitrogen atmosphere, precipitating in diethyl ether, and drying in vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the quaternary ammonium salt hydrophilic polymer prepared in the step (1), 2.5g of hydroxyl-terminated polydimethylsiloxane with the dynamic viscosity of 40000mPa & s, 0.3g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12h to obtain the silicone gel anti-fouling and antibacterial coating filled with the glass beads.
Example 2
(1) Adding 0.78g (0.004mol) of 3-mercaptopropyltrimethoxysilane, 4.18g (0.015mol) of methacryloyloxyethylbenzyldimethylammonium chloride, 3.25g (0.0117mol) of sulfobetaine methacrylate and 20g of trifluoroethanol into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting at 80 ℃ for 12h under the nitrogen atmosphere, precipitating in diethyl ether, and drying in vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.3g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with glass beads.
Example 3
(1) Adding 0.78g (0.004mol) of 3-mercaptopropyltrimethoxysilane, 4.18g (0.015mol) of methacryloyloxyethyl benzyl dimethyl ammonium chloride, 3.25g (0.011mol) of methacryloyloxyethyl phosphorylcholine and 20g of dichloroethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azo-bis-isobutyronitrile, reacting at 80 ℃ for 12h under the nitrogen atmosphere, precipitating in diethyl ether, and drying under vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.3g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with glass beads.
Example 4
(1) Adding 0.78g (0.004mol) of 3-mercaptopropyltrimethoxysilane, 4.18g (0.012mol) of methacryloyloxyethyl n-dodecyl dimethyl ammonium bromide, 3.25g (0.011mol) of methacryloyloxyethyl phosphorylcholine and 20g of dichloroethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azodiisobutyronitrile, reacting at 80 ℃ for 12h under the atmosphere of nitrogen, precipitating in diethyl ether, and drying under vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.3g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with glass beads.
Example 5
(1) Adding 0.78g (0.004mol) of 3-mercaptopropyltrimethoxysilane, 4.18g (0.010mol) of acryloyloxyethyl-n-hexadecyl dimethyl ammonium bromide, 3.25g (0.011mol) of methacryloyloxyethyl phosphorylcholine and 20g of dichloroethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting at 80 ℃ for 12h under the nitrogen atmosphere, precipitating in diethyl ether, and drying under vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.3g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with glass beads.
Example 6
(1) Adding 0.59g (0.003mol) of 3-mercaptopropyltrimethoxysilane, 3.98g (0.0095mol) of methacryloyloxyethyl n-hexadecyldimethylammonium bromide, 2.80g (0.0069mol) of polyethylene glycol monomethyl ether-methacrylate and 20g of dichloromethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting at 80 ℃ for 12h under the atmosphere of nitrogen, precipitating in diethyl ether, and drying under vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.5g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with glass beads.
Example 7
(1) Adding 0.59g (0.003mol) of 3-mercaptopropyltrimethoxysilane, 3.98g (0.0095mol) of methacryloyloxyethyl n-hexadecyldimethyl ammonium bromide, 2.80g (0.01mol) of methacrylic sulfobetaine and 20g of trifluoroethanol into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting at 80 ℃ for 12h under the nitrogen atmosphere, precipitating in diethyl ether, and drying under vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.5g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with the glass beads.
Example 8
(1) Adding 0.59g (0.003mol) of 3-mercaptopropyltrimethoxysilane, 3.98g (0.0095mol) of methacryloyloxyethyl n-hexadecyldimethyl ammonium bromide, 2.80g (0.0096mol) of methacryloyloxyethyl phosphorylcholine and 20g of dichloroethane into a container, introducing nitrogen for 15min to remove air in a reaction bottle, adding 0.1g of initiator azobisisobutyronitrile, reacting at 80 ℃ for 12h in a nitrogen atmosphere, precipitating in diethyl ether, and drying in vacuum to obtain the quaternary ammonium salt hydrophilic polymer.
(2) Adding 0.35g of the prepared quaternary ammonium salt hydrophilic polymer, 2.5g of hydroxyl-terminated polydimethylsiloxane with the viscosity of 40000mPa & s, 0.5g of glass beads, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene into a container, uniformly mixing at room temperature, coating on a glass slide, and curing at room temperature for 12 hours to obtain the silicone gel anti-fouling antibacterial coating filled with the glass beads.
Comparative example 1
The preparation process was substantially the same as in example 1 except that the organic solvent in step (1) was replaced with acetonitrile.
According to observation, in the reaction process, after a period of reaction, a gel phenomenon appears in the reactor, and the reaction can not be continued.
Comparative example 2
The preparation process was substantially the same as in example 1 except that 0.3g of glass beads were not added in step (2).
Comparative example 3
The preparation process was substantially the same as in example 2 except that 0.3g of glass beads was not added in step (2).
Comparative example 4
The preparation process was substantially the same as in example 3 except that 0.3g of glass beads were not added in step (2).
Comparative example 5
2.5g of hydroxyl-terminated polydimethylsiloxane with the dynamic viscosity of 50000mPa & s, 0.15g of tetraethyl orthosilicate, 0.04g of bismuth laurate and 10g of dimethylbenzene are added into a container, are uniformly mixed at room temperature, are coated on a glass slide, and are cured for 12 hours at room temperature to obtain the silicone gel anti-fouling and antibacterial coating filled with glass beads.
And (3) performance testing:
1. the sterilization rate test method comprises the following steps: the coating samples prepared in each of examples and comparative examples were exposed to 5mL of E.coli culture solution (concentration: about 109CFU/mL, where the growth rate of bacteria is the fastest) with OD 1, incubated at 37 ℃ for 3 hours, diluted stepwise, and 10 was taken-6，10-5，10-4，10-3Respectively coating 20 μ L of gradient bacterial liquid on solid plate culture medium at 37 deg.CAnd culturing for 24h, and counting viable bacteria on a flat plate with the colony number of about 10-100 to obtain the concentration of the contacted viable bacteria (namely the colony forming number, CFU/mL, which is in direct proportion to the original bacteria number).
The number of kill was calculated as follows:
the sterilization rate (%) - (original bacteria count-viable bacteria count)/original bacteria count × 100%
And (3) testing results:
the results of the tests on the bactericidal rate of the coatings prepared respectively in each example are shown in table 1 below, and the results of the tests on the bactericidal rate of the coatings prepared respectively in each comparative example are shown in table 2 below.
TABLE 1
TABLE 2
As can be seen from the table above, the silicone gel anti-fouling and antibacterial coating filled with glass beads, prepared by the invention, has a bactericidal rate of over 60% on escherichia coli, and shows that the coating has strong bactericidal performance.
2. Anti-protein adsorption test method:
bovine Serum Albumin (BSA) is dissolved in a phosphate buffer saline solution to prepare BSA solutions with the concentrations of 0.2, 0.5, 0.8, 1.0, 1.4 and 2.0g/L, namely BSA standard solutions. The absorbance at 280nm of the BSA buffer solution at each concentration was measured by an ultraviolet spectrophotometer. And (3) plotting by taking the BSA concentration as an abscissa and the absorbance as an ordinate, and calculating to obtain a linear simulation equation, namely the BSA absorbance standard curve in the concentration range.
The coatings prepared in each example and comparative example were placed in a six-well plate, 5mL of a 1g/L BSA solution was added, and static adsorption was carried out at a constant temperature of 25 ℃ for 24 hours. Samples were removed and the absorbance at 280nm of each solution in the six-well plate was measured using a UV spectrophotometer. The absorbance and the standard curve gave the concentration of BSA for each solution. The amount of BSA adsorbed per unit area of the sample was calculated from the change in BSA concentration.
The results of the BSA protein adsorption test for the coatings prepared in each example are shown in table 3 below, and the results of the BSA protein adsorption test for the coatings prepared in each comparative example are shown in table 4 below.
TABLE 3
TABLE 4
As can be seen from the table above, in the bovine serum albumin adsorption resistance test, the adsorption amount of the protein on the surface of the anti-fouling and antibacterial silicone gel coating filled with the glass beads is remarkably reduced, an excellent anti-protein adsorption effect is shown, and the coating is beneficial to fouling resistance.
3. Elastic modulus test method:
the coatings prepared in each example and comparative example were each formed into dumbbell-shaped coated bars, and the coated bars were subjected to a tensile test at room temperature using a Zwick/Roell Z020 universal material tester, Zwick, Germany, at a tensile rate of 10mm/min, and the test was repeated at least five times for each sample.
The results of the modulus of elasticity tests for the coated bars prepared in each example are shown in Table 5 below, and the results of the modulus of elasticity tests for the coated bars prepared in each comparative example are shown in Table 6 below.
TABLE 5
TABLE 6
| Numbering | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Modulus of elasticity/MPa | — | 1.11 | 1.25 | 1.15 | 0.93 |
An increase in the modulus of elasticity means an increase in the mechanical properties. As can be seen from the above table, the elastic modulus of the silicone gel anti-fouling antibacterial coating spline filled with the glass beads prepared by the invention is larger than that of a pure polysiloxane sample and that of a silicone gel anti-fouling antibacterial coating sample not filled with the glass beads, which shows that the mechanical strength of the modified coating is enhanced, and the introduction of the glass beads is beneficial to improving the mechanical performance of the coating.
Claims (10)
1. A preparation method of a silicone gel anti-fouling bacteriostatic coating filled with glass beads is characterized by comprising the following steps:
(1) mixing a quaternary ammonium salt monomer containing reactive double bonds, a hydrophilic monomer, a mercapto silane coupling agent and an organic solvent A, and initiating by an initiator under an inert atmosphere to prepare a quaternary ammonium salt hydrophilic polymer;
the quaternary ammonium salt monomer containing reactive double bonds is selected from one or more of methacryloyloxyethyl benzyl dimethyl ammonium chloride, methacryloyloxyethyl n-dodecyl dimethyl ammonium bromide, methacryloyloxyethyl n-hexadecyl dimethyl ammonium bromide, acryloyloxyethyl benzyl dimethyl ammonium chloride, acryloyloxyethyl n-dodecyl dimethyl ammonium bromide and acryloyloxyethyl n-hexadecyl dimethyl ammonium bromide;
the structural formulas of the hydrophilic monomers are respectively shown in the following formulas (I-1) to (I-6):
wherein x and y are independently selected from 3 to 25;
(2) and (2) blending the quaternary ammonium salt hydrophilic polymer prepared in the step (1), polysiloxane, a catalyst, glass beads, a cross-linking agent which can be selectively added and an organic solvent B, and coating and curing to obtain the silicone gel anti-fouling and antibacterial coating filled with the glass beads.
2. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 1, characterized in that in step (1):
the mercapto silane coupling agent is selected from one or more of mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane;
the organic solvent A is selected from one or more of dichloromethane, dichloroethane, trifluoroethanol and trifluorobutanol;
the molar ratio of the quaternary ammonium salt monomer containing the reactive double bond to the hydrophilic monomer is 0.05-5: 1;
the using amount of the mercapto silane coupling agent is 1-50% of the total molar amount of the monomers;
the dosage of the organic solvent A is 1-5 times of the total weight of the reactants.
3. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 1, characterized in that in step (1):
the initiator is selected from one or more of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobisisobutyronitrile, azobiscyclohexyl and azobisisobutyric acid;
the adding mass of the initiator is 0.1-5.0% of the total weight of the monomers.
4. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 1, characterized in that in step (1):
the hydrophilic monomer is selected from the group consisting of the above formulas (I-3) to (I-6).
5. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 4, characterized in that in step (1):
the quaternary ammonium salt monomer containing reactive double bonds is selected from one or more of methacryloyloxyethyl n-dodecyl dimethyl ammonium bromide, methacryloyloxyethyl n-hexadecyl dimethyl ammonium bromide, acryloyloxyethyl n-dodecyl dimethyl ammonium bromide and acryloyloxyethyl n-hexadecyl dimethyl ammonium bromide.
6. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 1, characterized in that in step (2):
the polysiloxane is selected from polydimethylsiloxane or hydroxymethyl-terminated polydimethylsiloxane, and the dynamic viscosity is 500-100000 mPa & s;
the catalyst is selected from an organic bismuth catalyst or an organic tin catalyst;
the cross-linking agent is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate;
the organic solvent B is selected from one or more of trifluoroethanol, trifluorobutanol, xylene, toluene, dichloromethane, methane and acetonitrile.
7. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 1, characterized in that in step (2):
the weight ratio of the quaternary ammonium salt hydrophilic polymer to the polysiloxane is 1-30: 100, respectively;
the mass of the glass beads is 1-20% of the total weight of the polymer;
the mass of the selectively added cross-linking agent is 1-15% of the total weight of the polymer;
the mass of the catalyst is 0.05-5.00% of the total weight of the polymer;
the dosage of the organic solvent B is 1-5 times of the total weight of the reactants.
8. The method for preparing a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 7, characterized in that in step (2):
the mass of the glass beads is 10-20% of the total weight of the polymer.
9. A glass bead filled silicone gel anti-fouling bacteriostatic coating prepared according to the method of any one of claims 1 to 8.
10. Use of a glass bead filled silicone gel anti-fouling bacteriostatic coating according to claim 9 in the marine anti-fouling, biomedical field.
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