CN115594851B - Reactive amphiphilic additive and preparation method and application thereof - Google Patents

Reactive amphiphilic additive and preparation method and application thereof Download PDF

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CN115594851B
CN115594851B CN202211347188.8A CN202211347188A CN115594851B CN 115594851 B CN115594851 B CN 115594851B CN 202211347188 A CN202211347188 A CN 202211347188A CN 115594851 B CN115594851 B CN 115594851B
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ester
methyl
fluorocarbon
amphiphilic additive
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CN115594851A (en
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马春风
潘健森
胡朋
谢庆宜
张国梁
张广照
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South China University of Technology SCUT
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
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    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
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Abstract

The invention discloses a reactive amphiphilic additive and a preparation method and application thereof. The reactive amphiphilic additive is prepared from the following components in parts by weight: 1-40 parts of fluorocarbon ester-anti-fouling monomer telomer; 10-60 parts of dichlorosilane; 10-50 parts of organic solvent; 0.1-10 parts of end capping agent; 1-60 parts of water. The reactive amphiphilic additive can be self-enriched on the surface of a coating in the film forming process, so that an ideal antifouling effect can be achieved by adding a small amount of the reactive amphiphilic additive; meanwhile, the coating body keeps the original high adhesive property and mechanical strength. In addition, the additive is fixed in the coating system by chemical reaction with the matrix resin, and is not released to the environment, thus having the characteristic of being ecological.

Description

Reactive amphiphilic additive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of antifouling materials, and particularly relates to a reactive amphiphilic additive, and a preparation method and application thereof.
Background
Biofouling is a troublesome problem in the fields of marine antifouling, biomedical and the like. The development of environmentally friendly anti-fouling coatings has become an important direction of research in recent years. The prior antifouling coating systems usually contain heavy metals or organic biocides, which have an adverse effect on the ecological environment. Polyurethane or silicone is a main material of a commonly used environment-friendly type antifouling coating, however, its surface lacks an antifouling function. The introduction of anti-fouling groups such as amphiphilic additives, zwitterions, quaternary ammonium salts, anti-fouling agents, etc. into the coating is an effective method. For example, there have been many studies reporting blending or grafting amphiphilic additives into polyurethane or Polydimethylsiloxane (PDMS). However, blending can cause the additive to be released continuously, resulting in reduced anti-fouling performance and environmental impact; in the graft system, however, most of the additive is embedded in the coating body, and therefore the stain resistance cannot be exhibited. Therefore, the development of an amphiphilic additive which can be self-enriched on the surface and not released is of great importance.
Disclosure of Invention
The invention aims at providing a reactive amphiphilic additive aiming at the defects of the existing antifouling materials and technologies. The reactive amphiphilic additive can meet the requirements of ecological friendly pollution prevention, static pollution prevention and long-acting pollution prevention.
Another object of the present invention is to provide a method for preparing the above reactive amphiphilic additive.
It is a further object of the present invention to provide the use of the reactive amphiphilic additive described above.
The above object of the present invention is achieved by the following technical scheme:
the reactive amphiphilic additive is prepared from the following components in parts by weight:
1-40 parts of fluorocarbon ester-anti-fouling monomer telomer;
10-60 parts of dichlorosilane;
10-50 parts of organic solvent;
0.1-10 parts of end capping agent;
1-60 parts of water;
the reactive amphiphilic additive is preferably prepared from the following components in parts by weight:
5-15 parts of fluorocarbon ester-anti-fouling monomer telomer;
20-30 parts of dichlorosilane;
5-20 parts of organic solvent;
1-5 parts of end capping agent;
40-60 parts of water;
the fluorocarbon ester-anti-fouling monomer telomer is prepared from the following components in parts by weight:
10-70 parts of (methyl) acrylic acid fluorocarbon ester;
10-70 parts of (methyl) acrylic ester anti-fouling monomer;
1-40 parts of sulfhydryl silane coupling agent;
1-60 parts of a solvent;
1-30 parts of an initiator;
the fluorocarbon ester-anti-fouling monomer telomer is preferably prepared from the following components in parts by weight:
18-60 parts of (methyl) acrylic acid fluorocarbon ester;
10-40 parts of (methyl) acrylic ester anti-fouling monomer;
4-40 parts of sulfhydryl silane coupling agent;
14.5-30 parts of solvent;
1-5 parts of an initiator;
the molecular weight of the fluorocarbon ester-anti-fouling monomer telomer is preferably 1000-10000 g/mol; more preferably 2000 to 4200g/mol.
In the fluorocarbon ester-anti-fouling monomer telomer:
the (methyl) acrylic acid fluorocarbon ester is acrylic acid fluorocarbon ester or methacrylic acid fluorocarbon ester;
the fluorocarbon acrylate preferably comprises at least one of trifluoroethyl acrylate, tetrafluoropropyl acrylate, hexafluorobutyl acrylate, nonafluorohexyl acrylate, dodecafluoroheptyl acrylate and 1H, 2H-heptadecafluorodecyl acrylate;
the fluorocarbon methacrylate preferably comprises at least one of trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, 1H, 2H-nonafluorohexyl methacrylate, dodecafluoroheptyl methacrylate and heptadecafluorodecyl methacrylate;
the structure of the (methyl) acrylic ester anti-fouling monomer contains carbon-carbon double bonds, and the polymerization degree of the (methyl) acrylic ester anti-fouling monomer is 1-10.
The (methyl) acrylic ester anti-fouling monomer is acrylic ester or methacrylic ester with anti-fouling activity; preferably polyethylene glycol acrylate (1) (the polymerization degree n is preferably 1 to 10 and n is an integer), ethyl carboxylic betaine acrylate (2), dimethylaminoethyl acrylate (3), benzisothiazolinone acrylate (4), bromopyrrolopyrrole nitrile acrylate (5), triclosan acrylate (6), capsaicin acrylate (7), polyethylene glycol methacrylate (8) (the polymerization degree n is preferably 1 to 10 and n is an integer), ethyl carboxylic betaine methacrylate (9), dimethylaminoethyl methacrylate (10), benzisothiazolinone methacrylate (11), bromopyrrolopyrrole nitrile methacrylate (12), triclosan propyl methacrylate (13) and capsaicin methacrylate (14); the chemical structural formula of the (methyl) acrylic ester anti-fouling monomer is shown as follows:
the mercapto silane coupling agent is preferably at least one of mercapto propyl methyl dimethoxy silane, mercapto methyl diethoxy silane, 3-mercapto propyl methyl diethoxy silane, mercapto methyl triethoxy silane and 3-mercapto propyl triethoxy silane.
The solvent is preferably at least one of toluene, xylene, isopropanol, methyl isobutyl ketone, acetone, ethyl acetate, butanone and butyl acetate.
The initiator is preferably at least one of azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
The reactive amphiphilic additive comprises the following components:
the dichlorosilane is preferably at least one of dimethyldichlorosilane, methylphenyl dichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane, methyltrifluoropropyldichlorosilane and diethyldichlorosilane; more preferably at least one of dimethyldichlorosilane and diphenyldichlorosilane.
The organic solvent is preferably at least one of tetrahydrofuran, acetone and N, N-dimethylformamide.
The end-capping agent is preferably at least one of hexamethyldisiloxane, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane, oligomeric hydroxyl silicone oil, oligomeric amino-terminated silicone oil, oligomeric mercapto silicone oil and oligomeric carboxyl silicone oil; more preferably at least one of hexamethyldisiloxane, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane and 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane.
The water is preferably deionized water.
The reactive amphiphilic additive has the following structure:
wherein C represents an end group, which may be NH 2 Any one of, COOH, SH, OH and Si-OH; a represents the content of fluorocarbon ester-anti-fouling monomer telomer, b represents the content of dichlorosilane; A-B are (methyl) in fluorocarbon ester-anti-fouling monomer telomerFluorocarbon acrylate and (meth) acrylate anti-fouling monomer structures. The structure of the reactive amphiphilic additive enables the surface energy of the reactive amphiphilic additive to be low, and the reactive amphiphilic additive can be preferentially enriched on the surface of a coating in the film forming process.
The preparation method of the reactive amphiphilic additive comprises the following steps:
(1) Mixing and reacting (methyl) acrylic acid fluorocarbon ester, (methyl) acrylic acid ester anti-fouling monomer, mercapto silane coupling agent, initiator and solvent to obtain fluorocarbon ester-anti-fouling monomer telomer;
(2) And mixing fluorocarbon ester-anti-fouling monomer telomer, dichlorosilane, organic solvent and water for reaction, removing redundant water, and adding a blocking agent to obtain the reactive amphiphilic additive.
In the step (1), the reaction conditions are preferably 60-100 ℃ for 12-36 h; more preferably at 90 to 100 ℃ for 12 to 18 hours.
In the step (2), the reaction condition is preferably 60-100 ℃ for 12-36 h; more preferably at 60 to 100 ℃ for 12 to 24 hours.
The application of the reactive amphiphilic additive in marine antifouling and biomedical antibacterial antifouling is provided.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The reactive amphiphilic additive has lower surface energy, can be preferentially enriched on the surface of a coating in the film forming process, and can achieve ideal antifouling effect and provide lasting fouling resistance only by introducing a small amount of the reactive amphiphilic additive into a coating system.
(2) The reactive amphiphilic additive is connected into a coating system through chemical bonding, is not released into the marine environment, has no influence on marine ecology, and is environment-friendly. Moreover, the reactive amphiphilic additive can be enriched on the surface of the coating, so that the coating body maintains high adhesion performance and mechanical strength.
(3) The preparation method of the reactive amphiphilic additive is simple and feasible, has low cost, is suitable for industrial production, is small in amount and efficient, and has wide application prospects in the fields of marine antifouling coatings, biomedical treatment and the like.
(4) When the reactive amphiphilic additive is added into matrix resin, the reactive amphiphilic additive can be self-enriched on the surface of a coating, and has a small amount of high-efficiency characteristics; meanwhile, the reactive amphiphilic additive can react with matrix resin to be immobilized, cannot be released into the environment, and has the characteristic of being ecological.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
Polyethylene glycol acrylate (1) having an anti-fouling activity (the degree of polymerization n is preferably 1 to 10 and n is an integer), ethyl carboxylic acid betaine acrylate (2), dimethylaminoethyl acrylate (3), benzisothiazolinone acrylate (4), bromopyrrolopyrrole nitrile acrylate (5), triclosan acrylate (6), capsaicin acrylate (7), polyethylene glycol methacrylate (8) (the degree of polymerization n is preferably 1 to 10 and n is an integer), ethyl carboxylic acid betaine methacrylate (9), dimethylaminoethyl methacrylate (10), benzisothiazolinone methacrylate (11), bromopyrrolopyrrole nitrile methacrylate (12), triclosan propyl methacrylate (13) and capsaicin methacrylate (14) are synthesized as follows:
polyethylene glycol acrylate (1) was purchased from Sigma Aldrich company (polyethylene glycol monomethyl ether monoacrylate);
the ethyl carboxylic betaine acrylate (2) is prepared by reacting ethyl acrylate with 2- (methylamino) ethanol and then reacting with acryloyl chloride, and the specific method refers to patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
dimethylaminoethyl acrylate (3) was purchased from Sigma Aldrich company (2- (dimethylamino) ethyl acrylate);
benzisothiazolinone acrylate (4) is prepared by reacting benzisothiazolinone monomer with formaldehyde and then with acryloyl chloride, specific method reference Biodegradable Poly (ester-co-acrylate) with Antifoulant PendantGroups for Marine Anti-biofouling. Acs appl. Mater. Interface 2019,11,11947-11953;
the bromopyrrocarbonitrile acrylic acid ester (5) is prepared by the reaction of bromopyrrocarbon and acryloyl chloride, and specifically comprises the following components: 6.99g (20 mmol) of bromopyrrocarbonitrile is dissolved in 20mL of dichloromethane and placed in a three-necked flask, 2.44g (24 mmol) of methacryloyl chloride and 2.43g (24 mmol) of triethylamine are slowly added dropwise at the same time for reaction in an ice water bath for 4 hours; after the reaction is finished, extracting with saturated saline water for three times, removing the solvent, and drying to obtain bromopyrrocarbonitrile acrylate; other conventional methods for preparing bromopyrrocarbonitrile acrylates are also suitable for use in the present application;
triclosan acrylic ester (6) is prepared by reacting triclosan with acryloyl chloride, and the specific method refers to patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
capsaicin acrylic ester (7) is prepared by reacting capsaicin (trans-8-methyl-N-vanillyl-6-nonenamide) with acryloyl chloride, and the specific method is shown in patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
polyethylene glycol methacrylate (8) was purchased from Sigma Aldrich company (poly (ethylene glycol) methacrylate);
the ethyl carboxylic acid betaine methacrylate (9) is prepared by reacting ethyl acrylate with 2- (methylamino) ethanol and then reacting with methacryloyl chloride, and the specific method refers to patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
dimethylaminoethyl methacrylate (10) was purchased from Sigma Aldrich company (ethyl 2- (dimethylamino) methacrylate);
benzisothiazolinone methacrylate (11) is prepared by reacting benzisothiazolinone monomer with formaldehyde and then with methacryloyl chloride, specific method reference Biodegradable Poly (ester-co-acrylate) with Antifoulant PendantGroups for Marine Anti-biofouling. Acs appl. Mater. Interfaces2019,11,11947-11953;
the bromopyrrocarbonitrile methacrylate (12) is prepared by reacting bromopyrrocarbonitrile with methacryloyl chloride, and specifically comprises: 6.99g (20 mmol) of bromopyrrocarbonitrile is dissolved in 20mL of dichloromethane and placed in a three-necked flask, 2.44g (24 mmol) of methacryloyl chloride and 2.43g (24 mmol) of triethylamine are slowly added dropwise at the same time for reaction in an ice water bath for 4 hours; after the reaction is finished, extracting with saturated saline water for three times, removing the solvent, and drying to obtain bromopyrrocarbonitrile acrylate; other conventional methods for preparing bromopyrrocarbonitrile acrylates are also suitable for use in the present application;
triclosan propyl methyl acrylate (13) is prepared by reacting triclosan with methacryloyl chloride, and the specific method is shown in patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
capsaicin methacrylate (14) is prepared by reacting capsaicin (trans-8-methyl-N-vanillyl-6-nonenamide) with methacryloyl chloride, and the specific method is shown in patent 201710245180.3, namely self-polishing zwitterionic antifouling resin with main chain degradability, and preparation and application thereof;
adhesion force: testing according to GB/T5210-2006 adhesion test of colored paint and varnish pulling method;
anti-human serum fibrinogen adsorption test procedure reference is made to MaJ, maC, zhang G.Degradable Polymer with Protein Resistance in a Marine Environment [ J ]. Langmuir,2015,31 (23): quartz Crystal Microbalance with Dissipation (QCM-D) portion 6471-6478;
anti-Pseudomonas aeruginosa adhesion test procedure is described in section Antibacterial Tests of Biodegradable Poly (ester-co-acrylate) with Antifoulant PendantGroups for Marine Anti-biofouling. ACS appl. Mater. Interface 2019,11, 11947-11953.
Example 1
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) 60 parts by mass of hexafluorobutyl acrylate, 20 parts by mass of an antifouling agent ethyl carboxylic betaine acrylate (2), 4 parts by mass of mercaptopropyl methyl dimethoxy silane, 1 part by mass of benzoyl peroxide and 15 parts by mass of ethyl acetate are added into a reaction vessel to react for 12 hours at 100 ℃ to obtain a fluorocarbon ester-antifouling monomer telomer, wherein the molecular weight is 2000g/mol.
(2) In a reactor, 9 parts by mass of fluorocarbon ester-anti-fouling monomer telomer is dissolved in 10 parts by mass of tetrahydrofuran, then the mixture and 30 parts by mass of diphenyl dichlorosilane are added into 50 parts by mass of deionized water reaction medium to react for 12 hours at 60 ℃, then deionized water is removed, and 1 part by mass of hexamethyldisiloxane is added to obtain the reactive amphiphilic additive, wherein the molecular weight of the reactive amphiphilic additive is 20000g/mol.
Performance test:
in a reaction vessel, 0.5 part by mass of a reactive amphiphilic additive, 0.1 part by mass of a dibutyltin dilaurate catalyst, 49.5 parts by mass of a siloxane-terminated polyurethane resin and 50 parts by mass of a tetrahydrofuran solvent are added, and after stirring for 3 hours at normal temperature, the mixture is coated on an epoxy plate and cured for 24 hours at 40 ℃ to obtain a coating. The adhesive force of the obtained coating film is 1.2MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 100%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 99%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 1.2MPa, the adsorption efficiency of anti-human serum fibrinogen is 3%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 7%.
Example 2
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) Into a reaction vessel, 30 parts by mass of trifluoroethyl acrylate, 20 parts by mass of octafluoropentyl methacrylate, 10 parts by mass of 1H, 2H-nonafluorohexyl methacrylate, 10 parts by mass of capsaicin methacrylate (14) as an antifouling agent, 10 parts by mass of 3-mercaptopropyl methyl diethoxysilane, 1 part by mass of azobisisobutyronitrile and 19 parts by mass of toluene were added to react at 100℃for 12 hours to obtain a fluorocarbon ester-antifouling monomer telomer having a molecular weight of 3000g/mol.
(2) In a reactor, 10 parts by mass of fluorocarbon ester-anti-fouling monomer telomer was dissolved in 20 parts by mass of tetrahydrofuran, then added to 49 parts by mass of deionized water reaction medium with 20 parts by mass of dimethyldichlorosilane, reacted at 70 ℃ for 12 hours, then deionized water was removed, and 1 part by mass of hexamethyldisiloxane was added to obtain a reactive amphiphilic additive having a molecular weight of 15000g/mol.
Performance test:
in a reaction vessel, 2 parts by mass of a reactive amphiphilic additive, 0.2 part by mass of a dibutyltin dilaurate catalyst, 37.8 parts by mass of a siloxane-terminated polyurethane resin and 60 parts by mass of a xylene solvent are added, stirred at normal temperature for 6 hours, then coated on an epoxy plate, and cured at 50 ℃ for 10 hours to obtain a coating. The adhesive force of the obtained coating film is 1.5MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 90%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 99%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 1.6MPa, the adsorption efficiency of anti-human serum fibrinogen is 2%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 5%. The result shows that the addition of the amphiphilic additive can obviously improve the anti-fouling performance of the coating while maintaining the original mechanical strength of the organosilicon coating.
Example 3
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) Into a reaction vessel, 10 parts by mass of octafluoropentyl methacrylate, 8 parts by mass of dodecafluoroheptyl methacrylate, 10 parts by mass of an antifouling agent of bromopyrrocarbonitrile acrylate (5), 40 parts by mass of mercaptomethyltriethoxysilane, 2 parts by mass of azobisisovaleronitrile, 30 parts by mass of isopropanol were added and reacted at 100℃for 12 hours to obtain a fluorocarbon ester-antifouling monomer telomer having a molecular weight of 4200g/mol.
(2) In a reactor, 6 parts by mass of fluorocarbon ester-anti-fouling monomer telomer is dissolved in 10 parts by mass of acetone, then added into 50 parts by mass of deionized water reaction medium together with 30 parts by mass of diphenyl dichlorosilane, reacted for 24 hours at 100 ℃, then deionized water is removed, and 4 parts by mass of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane is added to obtain a reactive amphiphilic additive, wherein the molecular weight of the reactive amphiphilic additive is 10000g/mol.
Performance test:
in a reaction vessel, 1.5 parts by mass of a reactive amphiphilic additive, 0.1 part by mass of a dibutyltin dilaurate catalyst, 43.5 parts by mass of a siloxane-terminated polyurethane resin and 55 parts by mass of a xylene solvent were added, stirred at normal temperature for 12 hours, then coated on an epoxy plate, and cured at 55 ℃ for 9 hours to obtain a coating. The adhesive force of the obtained coating film is 2.0MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 90%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 98%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 2.0MPa, the adsorption efficiency of anti-human serum fibrinogen is 3%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 6%.
Example 4
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) 15 parts by mass of 1H, 2H-nonafluorohexyl methacrylate, 10 parts by mass of 1H, 2H-heptadecafluorodecyl acrylate, 5 parts by mass of an anti-fouling agent polyethylene glycol methacrylate (8), 5 parts by mass of an anti-fouling agent dimethylaminoethyl methacrylate (10), 15 parts by mass of an anti-fouling agent bromopyrrolopyrrole nitrile methacrylate (12), 15 parts by mass of 3-mercaptopropyl triethoxysilane, 5 parts by mass of azobisisovaleronitrile, 15 parts by mass of methyl isobutyl ketone and 10 parts by mass of butyl acetate were added to a reaction vessel and reacted at 100 ℃ for 12 hours to obtain a fluorocarbon ester-anti-fouling monomer telomer having a molecular weight of 2200g/mol.
(2) In a reactor, 5 parts by mass of fluorocarbon ester-anti-fouling monomer telomer is dissolved in 5 parts by mass of acetone and 5 parts by mass of tetrahydrofuran, then the mixture and 20 parts by mass of diphenyl dichlorosilane are added into 60 parts by mass of deionized water reaction medium to react for 24 hours at 80 ℃, then deionized water is removed, and 5 parts by mass of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane is added to obtain a reactive amphiphilic additive, wherein the molecular weight of the reactive amphiphilic additive is 8000g/mol.
Performance test:
in a reaction vessel, 2.5 parts by mass of a reactive amphiphilic additive, 0.1 part by mass of a dibutyltin dilaurate catalyst, 57.5 parts by mass of a silicone-terminated polyurethane resin and 40 parts by mass of a xylene solvent were added, stirred at normal temperature for 6 hours, then coated on an epoxy plate, and cured at 55 ℃ for 12 hours to obtain a coating. The adhesive force of the obtained coating film is 1.8MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 98%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 96%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 1.9MPa, the adsorption efficiency of anti-human serum fibrinogen is 9%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 12%.
Example 5
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) 15 parts by mass of trifluoroethyl acrylate, 15 parts by mass of octafluoropentyl methacrylate, 11 parts by mass of 1H, 2H-nonafluorohexyl methacrylate, 12 parts by mass of an antifouling agent polyethylene glycol acrylate (1), 11 parts by mass of an antifouling agent triclosan acrylate (6), 11 parts by mass of an antifouling agent capsaicin methacrylate (14), 10 parts by mass of 3-mercaptopropyl triethoxysilane, 0.5 part by mass of di-t-butyl peroxide and 14.5 parts by mass of xylene are added into a reaction vessel, and reacted at 100 ℃ for 12 hours to obtain a fluorocarbon ester-antifouling monomer telomer with a molecular weight of 2800g/mol.
(2) In a reactor, 10 parts by mass of fluorocarbon ester-anti-fouling monomer telomer was dissolved in 10 parts by mass of tetrahydrofuran and 10 parts by mass of N, N-dimethylformamide, then added to 40 parts by mass of diphenyldichlorosilane, reacted at 90 ℃ for 24 hours, and then deionized water was removed, and 10 parts by mass of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane and 5 parts by mass of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane were added to obtain a reactive amphiphilic additive having a molecular weight of 15000g/mol.
Performance test:
in a reaction vessel, 5 parts by mass of a reactive amphiphilic additive, 0.1 part by mass of a dibutyltin dilaurate catalyst, 50 parts by mass of a siloxane-terminated polyurethane resin and 45 parts by mass of a xylene solvent are added, stirred at normal temperature for 24 hours, then coated on an epoxy plate, and cured at 60 ℃ for 12 hours to obtain a coating. The adhesive force of the obtained coating film is 2.5MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 100%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 99%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 2.5MPa, the adsorption efficiency of anti-human serum fibrinogen is 8%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 10%.
Example 6
A method for preparing a reactive amphiphilic additive, comprising the steps of:
(1) Adding 10 parts by mass of tetrafluoropropyl methacrylate, 10 parts by mass of 1H, 2H-heptadecafluorodecyl acrylate, 10 parts by mass of dodecafluoroheptyl acrylate, 15 parts by mass of an antifouling agent dimethylaminoethyl acrylate (3), 10 parts by mass of an antifouling agent benzisothiazolinone methacrylate (11), 15 parts by mass of an antifouling agent triclosan-propyl methacrylate (13), 10 parts by mass of 3-mercaptopropyl methyl diethoxysilane, 5 parts by mass of tert-butyl peroxy-2-ethylhexanoate and 15 parts by mass of butanone into a reaction vessel, and reacting at 90 ℃ for 18 hours to obtain a fluorocarbon ester-antifouling monomer telomer with a molecular weight of 3500g/mol;
(2) In a reactor, 15 parts by mass of fluorocarbon ester-anti-fouling monomer telomer is dissolved in 20 parts by mass of N, N-dimethylformamide, then the mixture and 20 parts of diphenyl dichlorosilane are added into 40 parts by mass of deionized water reaction medium to react for 12 hours at 60 ℃, then deionized water is removed, and 5 parts by mass of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane is added to obtain a reactive amphiphilic additive, wherein the molecular weight of the reactive amphiphilic additive is 5000g/mol.
Performance test:
in a reaction vessel, 1 part by mass of a reactive amphiphilic additive, 0.1 part by mass of a dibutyltin dilaurate catalyst, 49 parts by mass of a siloxane-terminated polyurethane resin and 50 parts by mass of a xylene solvent are added, and after stirring for 18 hours at normal temperature, the mixture is coated on an epoxy plate and cured for 24 hours at 35 ℃ to obtain a coating. The adhesive force of the obtained coating film is 1.6MPa, the adsorption efficiency of the anti-human serum fibrinogen reaches 95%, and the adhesion efficiency of the anti-pseudomonas aeruginosa reaches 90%. The amphiphilic additive control coating is not contained, the adhesive force of a paint film is 1.5MPa, the adsorption efficiency of anti-human serum fibrinogen is 1%, and the adhesion efficiency of anti-pseudomonas aeruginosa is 1%.
The performance test results of the reactive amphiphilic additives prepared in examples 1-6 show that the addition of the amphiphilic additives remarkably improves the anti-fouling performance of the coating while maintaining the original adhesion performance and mechanical strength of the organosilicon coating.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The reactive amphiphilic additive is characterized by being prepared from the following components in parts by weight:
1-40 parts of fluorocarbon ester-anti-fouling monomer telomer;
10-60 parts of dichlorosilane;
10-50 parts of organic solvent;
0.1-10 parts of end capping agent;
1-60 parts of water;
the fluorocarbon ester-anti-fouling monomer telomer comprises the following components in parts by weight:
10-70 parts of (methyl) acrylic acid fluorocarbon ester;
10-70 parts of (methyl) acrylic ester anti-fouling monomer;
1-40 parts of sulfhydryl silane coupling agent;
1-60 parts of a solvent;
1-30 parts of an initiator;
the molecular weight of the fluorocarbon ester-anti-fouling monomer telomer is 1000-10000 g/mol;
the (methyl) acrylic acid fluorocarbon ester is acrylic acid fluorocarbon ester or methacrylic acid fluorocarbon ester;
the (methyl) acrylic ester anti-fouling monomer is acrylic ester or methacrylic ester with anti-fouling activity.
2. The reactive amphiphilic additive according to claim 1, which is prepared from the following components in parts by mass:
5-15 parts of fluorocarbon ester-anti-fouling monomer telomer;
20-30 parts of dichlorosilane;
5-20 parts of organic solvent;
1-5 parts of end capping agent;
40-60 parts of water.
3. The reactive amphiphilic additive according to claim 1, characterized in that:
the fluorocarbon ester-anti-fouling monomer telomer is prepared from the following components in parts by weight:
18-60 parts of (methyl) acrylic acid fluorocarbon ester;
10-40 parts of (methyl) acrylic ester anti-fouling monomer;
4-40 parts of sulfhydryl silane coupling agent;
14.5-30 parts of solvent;
1-5 parts of an initiator;
the molecular weight of the fluorocarbon ester-anti-fouling monomer telomer is 2000-4200 g/mol.
4. The reactive amphiphilic additive according to claim 1, characterized in that:
the fluorocarbon acrylate comprises at least one of trifluoroethyl acrylate, hexafluorobutyl acrylate, nonafluorohexyl acrylate, dodecafluoroheptyl acrylate and 1H, 2H-heptadecafluorodecyl acrylate;
the fluorocarbon methacrylate comprises at least one of trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate, octafluoropentyl methacrylate, 1H, 2H-nonafluorohexyl methacrylate, dodecafluoroheptyl methacrylate and heptadecafluorodecyl methacrylate.
5. The reactive amphiphilic additive according to claim 1, characterized in that:
the (methyl) acrylic acid ester anti-fouling monomer is one or more than two of polyethylene glycol acrylic acid ester (1), ethyl carboxylic acid betaine acrylic acid ester (2), dimethylaminoethyl acrylic acid ester (3), benzisothiazolinone acrylic acid ester (4), bromo-pyrrole nitrile acrylic acid ester (5), triclosan acrylic acid ester (6), capsaicin acrylic acid ester (7), polyethylene glycol methacrylic acid ester (8), ethyl carboxylic acid betaine methacrylic acid ester (9), dimethylaminoethyl methacrylic acid ester (10), benzisothiazolinone methacrylic acid ester (11), bromo-pyrrole nitrile methacrylic acid ester (12), triclosan propyl methyl acrylic acid ester (13) and capsaicin methacrylic acid ester (14); the corresponding structural formula is as follows:
the polymerization degree n of the polyethylene glycol acrylic ester is 1-10, and n is an integer;
the polymerization degree n of the polyethylene glycol methacrylate is 1-10, and n is an integer.
6. The reactive amphiphilic additive according to claim 1, characterized in that:
the sulfhydryl silane coupling agent is at least one of sulfhydryl propyl methyl dimethoxy silane, sulfhydryl methyl diethoxy silane, 3-sulfhydryl propyl methyl diethoxy silane, sulfhydryl methyl triethoxy silane and 3-sulfhydryl propyl triethoxy silane;
the solvent is at least one of toluene, xylene, isopropanol, methyl isobutyl ketone, acetone, ethyl acetate, butanone and butyl acetate;
the initiator is at least one of azodiisobutyronitrile, azodiisovaleronitrile, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
7. The reactive amphiphilic additive according to claim 1, characterized in that:
the dichlorosilane is at least one of dimethyl dichlorosilane, methyl phenyl dichlorosilane, diphenyl dichlorosilane, methyl vinyl dichlorosilane, methyl trifluoro propyl dichlorosilane and diethyl dichlorosilane;
the organic solvent is at least one of tetrahydrofuran, acetone and N, N-dimethylformamide;
the end-capping agent is at least one of hexamethyldisiloxane, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane, oligomeric hydroxyl silicone oil, oligomeric amino-terminated silicone oil, oligomeric mercapto silicone oil and oligomeric carboxyl silicone oil.
8. A method for preparing the reactive amphiphilic additive according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
(1) Mixing and reacting (methyl) acrylic acid fluorocarbon ester, (methyl) acrylic acid ester anti-fouling monomer, mercapto silane coupling agent, initiator and solvent to obtain fluorocarbon ester-anti-fouling monomer telomer;
(2) And mixing fluorocarbon ester-anti-fouling monomer telomer, dichlorosilane, organic solvent and water for reaction, removing redundant water, and adding a blocking agent to obtain the reactive amphiphilic additive.
9. The method of preparing a reactive amphiphilic additive according to claim 8, wherein: the method comprises the following steps:
in the step (1), the reaction condition is that the reaction is carried out for 12-36 hours at the temperature of 60-100 ℃;
in the step (2), the reaction condition is that the reaction is carried out for 12-36 hours at the temperature of 60-100 ℃.
10. Use of a reactive amphiphilic additive according to any one of claims 1 to 7 in marine antifouling, biomedical antibacterial antifouling.
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