CN117487115B - Zwitterionic organosilicon polyoxime urethane antifouling resin and preparation method and application thereof - Google Patents

Zwitterionic organosilicon polyoxime urethane antifouling resin and preparation method and application thereof Download PDF

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CN117487115B
CN117487115B CN202311369411.3A CN202311369411A CN117487115B CN 117487115 B CN117487115 B CN 117487115B CN 202311369411 A CN202311369411 A CN 202311369411A CN 117487115 B CN117487115 B CN 117487115B
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zwitterionic
polyoxime
urethane
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organosilicon
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CN117487115A (en
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卢光明
王雪珍
田澍
王立平
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
    • C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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Abstract

The invention discloses a zwitterionic organosilicon polyoxime urethane antifouling resin and a preparation method and application thereof. The amphoteric ion organosilicon polyoxime urethane antifouling resin comprises self-repairing hard segments, sterilizing hard segments and organosilicon decontamination soft segments, wherein the self-repairing hard segments, the sterilizing hard segments and the organosilicon decontamination soft segments are connected through polyisocyanate and are alternately distributed; wherein the self-repairing hard segment comprises a dynamic bond unit, the sterilizing hard segment comprises a furyl dioxime unit, and the organosilicon decontamination soft segment is derived from zwitterionic modified polydimethylsiloxane. The zwitterionic silicone polyoxime urethane antifouling resin is suitable for being applied to surface antifouling of severe complex marine environment equipment, can effectively adhere marine fouling organisms, can realize autonomous repair of a coating after environmental mechanical damage, and prolongs the practical life of the coating.

Description

Zwitterionic organosilicon polyoxime urethane antifouling resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of antifouling, and in particular relates to zwitterionic organosilicon polyoxime urethane antifouling resin and a preparation method and application thereof.
Background
Marine biofouling is currently one of the most significant factors affecting ships and marine engineering equipment, causing marine economic losses, with annual delays in transportation, hull repair maintenance and cleaning costs of up to $1500 billion due to the attachment and accumulation of marine microorganisms, animals and plants. The active anti-fouling strategy of applying an anti-fouling coating to a surface is the simplest, economical and efficient method of solving marine fouling. However, the antifouling properties of most antifouling paints today stem from antifouling agents which are doped in the paint and have poisoning properties, especially cuprous oxide and part of the metal zinc containing antifouling agents which are widely used at present, and release of these antifouling agents into sea water will pose a great risk and hazard to the marine environment, ecological structures and human health. Therefore, the development of an antifouling resin having an intrinsic antibacterial property has become one of the important methods for solving the problems. In addition, for stationary ships or engineering equipment in the ocean, fouling organisms adhered to the surface are difficult to remove due to the lack of high-speed scouring action of water flow, so that the static fouling removal performance of the coating needs to be improved.
The marine environment is taken as a very complex environmental system, and the surface of the anti-fouling paint is inevitably threatened by various mechanical damages to cause the failure of the coating, so that the development of the anti-fouling paint capable of self-repairing in seawater has important significance. However, water molecules and ions in the high-salt seawater can inhibit the reconstruction and repair of molecular chains in the paint resin, and cause great difficulty for the development of self-repair anti-fouling resin and anti-fouling paint in the ocean.
Disclosure of Invention
The invention mainly aims to provide a zwitterionic organosilicon polyurethane anti-fouling resin, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
The embodiment of the invention provides a zwitterionic organosilicon polyoxime urethane antifouling resin, which comprises the following components: the self-repairing hard segment, the sterilizing hard segment and the organic silicon decontamination soft segment are connected through polyisocyanate and are alternately distributed; wherein the self-repairing hard segment comprises a dynamic bond unit, the sterilizing hard segment comprises a furyl dioxime unit, and the organosilicon decontamination soft segment is derived from zwitterionic modified polydimethylsiloxane.
The embodiment of the invention also provides a preparation method of the zwitterionic organosilicon polyurethane anti-fouling resin, which comprises the following steps:
prepolymerizing a prepolymerization system comprising polyisocyanate, zwitterionic modified polydimethylsiloxane, catalyst and solvent to obtain a prepolymer;
And mixing and reacting a compound for forming a self-repairing hard segment and a sterilizing hard segment with the prepolymer to prepare the zwitterionic silicone polyoxime urethane antifouling resin.
The embodiment of the invention also provides the application of the zwitterionic organosilicon polyoxime urethane antifouling resin in preparing self-healing antifouling paint under severe marine environment.
The embodiment of the invention also provides a self-healing method of the antifouling coating, which comprises the following steps:
Preparing an antifouling coating by adopting the zwitterionic silicone polyoxime urethane antifouling resin;
and soaking the antifouling coating with fracture or defect damage in saline water to enable the antifouling coating to self-heal.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the resin of the traditional antifouling paint, the zwitterionic organosilicon polyoxime ammonia ester antifouling resin has intrinsic antifouling performance, and can effectively contact and kill fouling organisms adhered to the surface through furan dioxime sterilization units in a molecular chain segment;
(2) Compared with the traditional antifouling paint resin, the zwitterionic silicone polyoxime alamine antifouling resin has static antifouling performance, and fouling organisms adhered to the surface are removed through a hydration layer formed by zwitterionic units in a molecular chain segment;
(3) Compared with the traditional antifouling paint resin, the zwitterionic organosilicon polyoxime ammonia ester antifouling resin has the marine environment self-healing performance, and the self-healing of the paint in high-salt seawater is realized through the self-healing units in the molecular chain segments.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of sulfobetaine-modified polydimethylsiloxane in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a sample sulfobetaine modified silicone polyoxime alamine resin according to example 1 of the present invention;
FIGS. 3 a-3 g are photographs showing the elongation of samples of examples 1-4 and comparative examples 1-3 of the present invention after 24 hours of repair in 3.5wt% NaCl aqueous solution;
FIGS. 4 a-4 h are graphs showing the bactericidal properties of coatings prepared from samples of examples 1-4 and comparative examples 1-3 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has provided a technical scheme of the present invention through long-term research and a great deal of practice, which mainly introduces dynamic bond units (hydrogen bond and disulfide bond) into the resin, and endows the resin with autonomous self-healing performance under high-salt sea water; introducing zwitterionic units (sulfobetaine, carboxybetaine, phosphorylcholine and the like) to endow the resin with the performance of dynamically removing fouling organisms; the introduction of a sterilization unit (furan dioxime) gives the resin contact fouling organism killing performance.
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Specifically, as one aspect of the technical scheme of the invention, the zwitterionic silicone polyoxime urethane antifouling resin comprises: the self-repairing hard segment, the sterilizing hard segment and the organic silicon decontamination soft segment are connected through polyisocyanate and are alternately distributed; wherein the self-repairing hard segment comprises a dynamic bond unit, the sterilizing hard segment comprises a furyl dioxime unit, and the organosilicon decontamination soft segment is derived from zwitterionic modified polydimethylsiloxane.
The dynamic bond unit (hydrogen bond and disulfide bond) in the zwitterionic organosilicon polyoxime ammonia ester antifouling resin provided by the invention endows the resin with autonomous self-healing performance under high-salt seawater, the zwitterionic unit (namely an organosilicon decontamination soft segment (sulfobetaine, carboxybetaine, phosphorylcholine and the like) endows the resin with dynamic fouling organism removal performance, and the sterilization unit (furan dioxime) endows the resin with contact fouling organism killing performance.
In some preferred embodiments, the zwitterionic modified polydimethylsiloxane is obtained by graft modification of polydimethylsiloxane with a zwitterionic compound.
Further, the zwitterionic compound includes any one or a combination of two or more of sulfobetaine, carboxybetaine, phosphorylcholine, and is not limited thereto.
Further, the polydimethylsiloxane includes a hydroxyl-terminated (vinylmethylsiloxane) -dimethylsiloxane copolymer and/or an amino-terminated (vinylmethylsiloxane) -dimethylsiloxane copolymer, and is not limited thereto.
Further, the zwitterionic modified polydimethylsiloxane is obtained by grafting a zwitterionic compound onto a molecular chain of the polydimethylsiloxane using at least one of a radical reaction, a click chemistry reaction, and a D-a addition reaction, and is not limited thereto.
Further, the molecular weight of the polydimethylsiloxane is 2000-20000 g/mol.
Further, the content of the vinyl methyl siloxane in the polydimethylsiloxane is 2-20wt%.
In some preferred embodiments, the zwitterionic modified polydimethylsiloxane includes, but is not limited to, a compound represented by a-n and a combination of two or more compounds represented by a-n:
Wherein n: m: and p: q=75 to 95:0.5 to 25:0.5 to 24.5:0.5 to 24.
In some preferred embodiments, the source of furanyldioxime units comprises any one or a combination of the following compounds of formulas A-F and isomers of the compounds of formulas A-F:
Wherein, the values of x and y are 0-5, and M is selected from Cu, zn or Ag.
In some preferred embodiments, the dynamic bond units are derived from 4,4 '-diaminodiphenyl disulfide and/or 4,4' -dihydroxydiphenyl disulfide, and are not limited thereto.
In some preferred embodiments, the polyisocyanate includes any one or a combination of two or more of diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), 1, 5-Naphthalene Diisocyanate (NDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI), m-Xylylene Diisocyanate (XDI), tetramethyl m-xylylene diisocyanate (TMXDI), 1, 4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate (HTDI), 1, 4-phenylene diisocyanate (PPDI), norbornane diisocyanate (NBDI), L-Lysine Diisocyanate (LDI), and the like.
In some preferred embodiments, the molar ratio of silicone desmutting soft segment, bactericidal hard stamp, self-healing hard stamp to polyisocyanate in the zwitterionic silicone polyoxime urethane antifouling resin is 1:0.5:0.5:1 to 1:2:2:4.
Another aspect of the embodiment of the present invention also provides a method for preparing the zwitterionic silicone polyoxime urethane antifouling resin, which includes:
prepolymerizing a prepolymerization system comprising polyisocyanate, zwitterionic modified polydimethylsiloxane, catalyst and solvent to obtain a prepolymer;
And mixing and reacting a compound for forming a self-repairing hard segment and a sterilizing hard segment with the prepolymer to prepare the zwitterionic silicone polyoxime urethane antifouling resin.
In some preferred embodiments, the compound for forming a self-healing hard segment includes, but is not limited to, 4 '-diaminodiphenyl disulfide and/or 4,4' -dihydroxydiphenyl disulfide.
In some preferred embodiments, the compound for forming the bactericidal hard segment is furandioxime selected from any one or a combination of two or more of the following structures:
Wherein, the values of x and y are 0-5, and M is selected from Cu, zn or Ag.
In some preferred embodiments, the catalyst includes any one or a combination of two or more of dibutyltin dilaurate, stannous octoate, dibutyltin di (dodecylsulfide), dibutyltin diacetate, and is not limited thereto.
In some preferred embodiments, the solvent includes any one or a combination of two or more of ethanol, methanol, isopropanol, toluene, xylene, N-hexane, cyclohexane, diethyl ether, petroleum ether, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N-dimethylformamide, N-dimethylacetamide, and is not limited thereto.
In some preferred embodiments, the molar ratio of polyisocyanate, zwitterionic modified polydimethylsiloxane to catalyst is from 1 to 4:1:0.02.
In some preferred embodiments, the molar ratio of the compound for forming self-healing hard segments, the compound for forming bactericidal hard segments to the prepolymer is from 0.5 to 2:0.5 to 2:2 to 5.
In some preferred embodiments, the temperature of the prepolymerization reaction is from 50℃to 90 ℃.
Further, the temperature of the prepolymerization reaction was 70 ℃.
In some preferred embodiments, the time of the prepolymerization is 3 to 12 hours.
Further, the time of the prepolymerization reaction was 5 hours.
In some preferred embodiments, the method of making comprises: and mixing a compound for forming the self-repairing hard segment and the sterilizing hard segment with a solvent, adding the prepolymer, reacting for 3-12 hours at 50-90 ℃, and drying to obtain the zwitterionic organosilicon polyoxime urethane antifouling resin.
Further, the obtained product is dried in vacuum for 24 to 96 hours at the temperature of between 90 and 150 ℃.
In some more specific embodiments, the method of making comprises: and mixing the compound forming the self-repairing hard segment and the sterilizing hard segment with a solvent, adding the mixture into the prepolymer, reacting for 5 hours at 70 ℃, and vacuum drying the obtained product at 90 ℃ for 24 hours to obtain the zwitterionic organosilicon polyoxime urethane antifouling resin.
In some more specific implementations, the method of preparing the zwitterionic silicone polyoxime urethane anti-fouling resin comprises:
(1) The following reactants were prepared: zwitterionic modified polydimethylsiloxane, polyisocyanate, dibutyl tin dilaurate (DBTDL), sterilized hard forging, self-repairing hard forging and solvent;
(2) Polyisocyanate and dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to the zwitterionic modified polydimethylsiloxane, which was stirred at 70℃for 5h to synthesize a prepolymer.
(3) Dissolving the sterilization hard forging and the self-repairing hard forging in a solvent, adding the solvent into the prepolymer, and stirring for 5 hours at 70 ℃ to obtain a target product;
(4) And (3) drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain the organosilicon polyoxime urethane resin.
Solvents of embodiments of the present invention include, but are not limited to, one or a combination of two or more of ethanol, methanol, isopropanol, toluene, xylene, N-hexane, cyclohexane, diethyl ether, petroleum ether, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N-dimethylformamide, N-dimethylacetamide, and are not limited thereto.
The zwitterionic silicone polyoxime urethane antifouling resin is suitable for being applied to surface antifouling of severe complex marine environment equipment, can effectively adhere marine fouling organisms, can realize autonomous repair of a coating after environmental mechanical damage, and prolongs the practical life of the coating.
The zwitterionic silicone polyoxime urethane antifouling resin has good bactericidal effect on escherichia coli, pseudomonas, vibrio, achromobacter, flavobacterium, spirochete, micrococcus, sarcina, bacillus, corynebacterium, cladosporium, nocardia and streptomyces.
Another aspect of an embodiment of the present invention also provides the use of the zwitterionic silicone polyoxime urethane anti-fouling resin described above in the preparation of an anti-fouling coating that self-heals in harsh marine environments.
Another aspect of the embodiments of the present invention also provides a self-healing method of an anti-fouling coating, comprising:
Preparing an antifouling coating by adopting the zwitterionic silicone polyoxime urethane antifouling resin;
And soaking the antifouling coating with fracture or defect damage in saline water to enable the antifouling coating to self-heal.
Further, the brine comprises a 3.5wt% aqueous nacl solution.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
Preparation of a sultaine modified silicone polyoxime urethane resin:
(1) The following reactants were prepared: sulfobetaine modified polydimethylsiloxane, isophorone diisocyanate, dibutyl tin dilaurate (DBTDL), furandioxime, 4' -diaminodiphenyl disulfide and tetrahydrofuran, wherein the structures of the zwitterionic modified polydimethylsiloxane are shown as the formula (1) and the furandioxime are shown as the formula (2) respectively:
(2) Uniformly mixing 3g of vinyl modified hydroxyl silicone oil with 0.3g of 3-dimethylamino-1-propanethiol, reacting at 60 ℃ for 24 hours, then dropwise adding 0.5g of 1, 3-propyl sultone into the system, and reacting at room temperature for 24 hours to obtain the sulfobetaine modified polydimethylsiloxane, wherein the nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 1.
(3) 0.5G isophorone diisocyanate and 0.01g dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6g sulfobetaine-modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(4) 0.2G of furan dioxime and 0.2g of 4,4' -diaminodiphenyl disulfide are dissolved in tetrahydrofuran and added to the prepolymer, and stirred at 70 ℃ for 5 hours to obtain the target product.
(5) Drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain the sulfobetaine modified organosilicon polyoxime urethane resin, wherein the structural formula of the resin is shown as follows:
the nuclear magnetic resonance hydrogen spectrum of the target product is shown in figure 2, which proves the successful synthesis of the product:
example 2
Preparation of a carboxy betaine modified organosilicon polyoxime urethane resin:
(1) The following reactants were prepared: carboxyl betaine modified polydimethylsiloxane, isophorone diisocyanate, dibutyl tin dilaurate (DBTDL), furandioxime, 4' -dihydroxydiphenyl disulfide and tetrahydrofuran, wherein the structures of the zwitterionic modified polydimethylsiloxane as shown in formula (4) and the furandioxime as shown in formula (5) are respectively shown in the following formulas:
(2) Uniformly mixing 3g of vinyl modified hydroxyl silicone oil with 0.3g of 3-dimethylamino-1-propanethiol, reacting for 24 hours at 60 ℃, then dropwise adding 0.5g of beta-propiolactone into the system, and reacting for 24 hours at room temperature to obtain the carboxyl betaine modified polydimethylsiloxane.
(3) 0.45G of isophorone diisocyanate and 0.01g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 5.5g of carboxybetaine-modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(4) 0.3G of furan dioxime and 0.3g of 4,4' -dihydroxydiphenyl disulfide are dissolved in tetrahydrofuran and added into the prepolymer, and the mixture is stirred for 5 hours at 70 ℃ to obtain the target product.
(5) Drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain the carboxyl betaine modified organosilicon polyoxime urethane resin, wherein the structural formula is shown as follows:
Example 3
Preparation of phosphorylcholine-modified organosilicon polyoxime urethane resin:
(1) The following reactants were prepared: phosphorylcholine modified polydimethylsiloxane, isophorone diisocyanate, dibutyl tin dilaurate (DBTDL), furandioxime, 4' -dihydroxydiphenyl disulfide and tetrahydrofuran, wherein the structures of the zwitterionic modified polydimethylsiloxane as shown in formula (7) and the furandioxime as shown in formula (8) are respectively shown in the following formulas:
(2) 3g of vinyl modified hydroxyl silicone oil and 0.3g of sulfhydryl methacryloxyethyl phosphorylcholine are uniformly mixed and reacted for 24 hours at 60 ℃ to obtain phosphorylcholine modified polydimethylsiloxane.
(3) 0.7G of isophorone diisocyanate and 0.01g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 6.6g of phosphorylcholine betaine-modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(4) 0.35G of furan dioxime and 0.33g of 4,4' -dihydroxydiphenyl disulfide are dissolved in tetrahydrofuran and added into the prepolymer, and the mixture is stirred for 5 hours at 70 ℃ to obtain the target product.
(5) Drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain phosphorylcholine modified organosilicon polyoxime urethane resin, wherein the structural formula is shown as follows:
Example 4
Preparation of a silicone polyoxime urethane resin modified based on carboxybetaine/sulfobetaine/phosphorylcholine:
(1) The following reactants were prepared: carboxyl betaine/sulfobetaine/phosphorylcholine modified polydimethylsiloxane, isophorone diisocyanate, dibutyl tin dilaurate (DBTDL), furandioxime, 4' -dihydroxydiphenyl disulfide and tetrahydrofuran, wherein the structures of the zwitterionic modified polydimethylsiloxane as shown in formula (13) and the furandioxime as shown in formula (14) are respectively shown in the following formulas:
(2) 3g of vinyl modified hydroxyl silicone oil, 0.2g of 3-dimethylamino-1-propanethiol and 0.1g of sulfhydryl methacryloxyethyl phosphorylcholine are uniformly mixed, reacted for 24 hours at 60 ℃, then 0.3g of 1, 3-propyl sultone and 0.3g of beta-propiolactone are added dropwise into the system, and reacted for 24 hours at room temperature, thus obtaining the carboxyl betaine/sulfobetaine/phosphorylcholine modified polydimethylsiloxane.
(3) 0.75G of isophorone diisocyanate and 0.02g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 7.8g of carboxybetaine/sulfobetaine/phosphorylcholine modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(4) 0.33G of furan dioxime, 0.22g of 4,4' -dihydroxydiphenyl disulfide were dissolved in tetrahydrofuran and added to the prepolymer, followed by stirring at 70℃for 5 hours, to obtain the objective product.
(5) Vacuum drying the target product at 90 ℃ for more than 24 hours to obtain the carboxyl betaine/sulfobetaine/phosphorylcholine modified organosilicon polyurethane resin, wherein the structural formula is shown as follows:
Comparative example 1
The process is the same as in example 2, except that a self-healing hard segment is absent;
(1) The following reactants were prepared: carboxyl betaine modified polydimethylsiloxane (same as in example 2), isophorone diisocyanate, dibutyltin dilaurate (DBTDL), furandioxime, tetrahydrofuran:
(2) 0.45g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 5.5g of carboxybetaine-modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(3) 0.6G of furan dioxime was dissolved in tetrahydrofuran and added to the prepolymer, and stirred at 70℃for 5 hours to obtain the objective product.
(4) Drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain the carboxyl betaine modified organosilicon polyoxime urethane resin lacking the self-repairing hard segment, wherein the structural formula of the resin is shown as the formula (16):
(16)
Comparative example 2
The process is the same as in example 2, except that the sterilization hard segment is absent;
(1) The following reactants were prepared: carboxyl betaine modified polydimethylsiloxane (same as in example 2), isophorone diisocyanate, dibutyltin dilaurate (DBTDL), 4' -diaminodiphenyl disulfide, tetrahydrofuran:
(2) 0.45g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 5.5g of carboxybetaine-modified polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(3) 0.6G of 4,4' -diaminodiphenyl disulfide was dissolved in tetrahydrofuran and added to the prepolymer, followed by stirring at 70℃for 5 hours, to obtain the objective product.
(4) Drying the target product in vacuum at 90 ℃ for more than 24 hours to obtain the carboxyl betaine modified organosilicon polyoxime urethane resin lacking a sterilization hard segment, wherein the structural formula of the resin is shown as the formula (17):
Comparative example 3
The process is the same as in example 2, except that the silicone desmear soft segment is absent;
(1) The following reactants were prepared: polydimethyl siloxane, isophorone diisocyanate, dibutyl tin dilaurate (DBTDL), furandioxime, 4' -diaminodiphenyl disulfide and tetrahydrofuran, wherein the structures of the zwitterionic modified polydimethyl siloxane shown in the formula (1) and the furandioxime shown in the formula (2) are respectively shown in the following formulas:
(2) 0.45g of isophorone diisocyanate and 0.01g of dibutyltin dilaurate (DBTDL) were dissolved in a solvent and added to 5.5g of polydimethylsiloxane, and stirred at 70℃for 5 hours to synthesize a prepolymer.
(3) 0.3G of furan dioxime, 0.3g of 4,4' -diaminodiphenyl disulfide were dissolved in tetrahydrofuran and added to the prepolymer, and stirred at 70℃for 5 hours to obtain the objective product.
(4) Vacuum drying the target product at 90 ℃ for more than 24 hours to obtain the organic silicon polyoxime urethane resin without a decontamination unit, wherein the structural formula of the organic silicon polyoxime urethane resin is shown as the formula (18):
(18)
Characterization of the properties:
Samples of examples 1-4 and comparative examples 1-3 were prepared as bars, then the bars were cut from the middle, the cut samples were aligned along a section in 3.5wt% NaCl water, and then after 24 hours of repair in this environment, they were removed. The removed bars were manually stretched to verify the self-healing of the sample in saline.
As shown in fig. 3 a-3 g, the repaired samples were all stretched, indicating that the broken and damaged bars were effectively repaired in saline.
Samples of examples 1-4 and comparative examples 1-3 were prepared into coatings, and the antimicrobial properties of the coating surfaces were tested by the GB/T31402-2015 method to verify the intrinsic antimicrobial properties of the coatings.
As shown in fig. 4a to 4h, the coatings prepared in examples 1 to 4 were 100% sterilized compared to the epoxy board (e.coli), and effective sterilization was achieved.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present invention is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present invention without departing from the spirit of the present invention and the scope of the claims are within the scope of the present invention.

Claims (20)

1. A zwitterionic silicone polyoxime urethane anti-fouling resin comprising: the self-repairing hard segment, the sterilizing hard segment and the organic silicon decontamination soft segment are connected through polyisocyanate and are alternately distributed; wherein the self-repairing hard segment comprises a dynamic bond unit, the sterilizing hard segment comprises a furyl dioxime unit, the organosilicon soil release soft segment is derived from zwitterionic modified polydimethylsiloxane obtained by grafting modification of polydimethylsiloxane with a zwitterionic compound, and the source of the furyl dioxime unit comprises any one or a combination of more than two of the following compounds:
Wherein, the values of x and y are 0 to 5, M is selected from Cu, zn or Ag;
the molar ratio of the organosilicon desmutting soft section, the sterilization hard forging, the self-repairing hard forging and the polyisocyanate in the zwitterionic organosilicon polyoxime urethane antifouling resin is 1:0.5:0.5:1 to 1:2:2:4.
2. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein:
the amphoteric ion compound is selected from any one or more than two of sulfobetaine, carboxyl betaine and phosphorylcholine.
3. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the polydimethylsiloxane is selected from hydroxyl-terminated vinyl methyl siloxane-dimethylsiloxane copolymer and/or amino-terminated vinyl methyl siloxane-dimethylsiloxane copolymer.
4. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the zwitterionic modified polydimethylsiloxane is obtained by grafting a zwitterionic compound onto a molecular chain of the polydimethylsiloxane by at least one of a free radical reaction, a click chemistry reaction, and a D-a addition reaction.
5. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the molecular weight of the polydimethylsiloxane is 2000-20000 g/mol.
6. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the content of vinyl methyl siloxane in the polydimethylsiloxane is 2-20wt%.
7. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the zwitterionic modified polydimethylsiloxane is selected from any one or more than two of the following structures:
Wherein n: m: and p: q=75 to 95:0.5 to 25:0.5 to 24.5:0.5 to 24.
8. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the dynamic bond units are derived from 4,4 '-diaminodiphenyl disulfide and/or 4,4' -dihydroxydiphenyl disulfide.
9. The zwitterionic silicone polyoxime urethane anti-fouling resin according to claim 1, wherein: the polyisocyanate is selected from any one or more than two of diphenylmethane diisocyanate, isoparaffin diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, m-xylylene diisocyanate, tetramethyl m-xylylene diisocyanate, 1, 4-cyclohexane diisocyanate, methylcyclohexane diisocyanate, 1, 4-xylylene diisocyanate, norbornane dimethylene isocyanate and L-lysine diisocyanate.
10. The method for producing a zwitterionic silicone polyoxime urethane antifouling resin according to any of claims 1 to 9, comprising:
prepolymerizing a prepolymerization system comprising polyisocyanate, zwitterionic modified polydimethylsiloxane, catalyst and solvent to obtain a prepolymer;
And mixing and reacting a compound for forming a self-repairing hard segment and a sterilizing hard segment with the prepolymer to prepare the zwitterionic silicone polyoxime urethane antifouling resin.
11. The method of manufacturing according to claim 10, wherein: the catalyst is selected from any one or more than two of dibutyl tin dilaurate, stannous octoate, dibutyl tin dilaurate and dibutyl tin diacetate.
12. The method of manufacturing according to claim 10, wherein: the solvent is selected from any one or more than two of ethanol, methanol, isopropanol, toluene, xylene, N-hexane, cyclohexane, diethyl ether, petroleum ether, methylene dichloride, chloroform, carbon tetrachloride, ethyl acetate, tetrahydrofuran, acetonitrile, N-dimethylformamide and N, N-dimethylacetamide.
13. The method of manufacturing according to claim 10, wherein: the molar ratio of the polyisocyanate, the zwitterionic modified polydimethylsiloxane and the catalyst is 1-4: 1:0.02.
14. The method of manufacturing according to claim 10, wherein: the mol ratio of the compound for forming self-repairing hard segment, the compound for forming sterilizing hard segment and the prepolymer is 0.5-2: 0.5 to 2:2 to 5.
15. The method of manufacturing according to claim 10, wherein: the temperature of the prepolymerization reaction is 50-90 ℃.
16. The method of manufacturing according to claim 10, wherein: the time of the prepolymerization reaction is 3-12 h.
17. The preparation method according to claim 10, characterized in that the preparation method comprises: and mixing a compound for forming the self-repairing hard segment and the sterilizing hard segment with a solvent, adding the prepolymer, reacting for 3-12 hours at 50-90 ℃, and drying to obtain the zwitterionic organosilicon polyoxime urethane antifouling resin.
18. The method of manufacturing according to claim 17, characterized in that the method of manufacturing comprises: and vacuum drying the obtained product at 90-150 ℃ for 24-96 h.
19. Use of a zwitterionic silicone polyoxime urethane antifouling resin according to any of claims 1-9 in the preparation of an antifouling coating which self-heals in harsh marine environments.
20. A method of self-healing an anti-fouling coating comprising:
Preparing an anti-fouling coating using the zwitterionic silicone polyoxime urethane anti-fouling resin of any one of claims 1-9;
and soaking the antifouling coating with fracture or defect damage in saline water to enable the antifouling coating to self-heal.
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