CN115074008A

CN115074008A - Organic silicon antifouling coating and preparation method thereof

Info

Publication number: CN115074008A
Application number: CN202210596324.0A
Authority: CN
Inventors: 刘月涛; 张德金; 赵素素; 宋程新; 高传慧; 武玉民
Original assignee: Qingdao University of Science and Technology
Current assignee: Qingdao University of Science and Technology
Priority date: 2022-05-27
Filing date: 2022-05-27
Publication date: 2022-09-20
Anticipated expiration: 2042-05-27
Also published as: CN116179066B; CN116179066A; CN115074008B; CN116285625A; CN116285625B

Abstract

The invention belongs to the field of corrosion protection of marine fouling organisms, and relates to an organic silicon antifouling coating and a preparation method thereof, wherein the preparation method comprises the following steps: the coating comprises an organic silicon-oxime urethane self-repairing antifouling coating based on nano silver, an organic silicon antifouling coating with fluorescent response and an organic silicon polyurethane marine antifouling coating containing a zwitterion side chain. The mechanical property of the material is improved by introducing AgNPs, the antifouling property is endowed to the material, and the antibacterial ability reaches 97.8%. According to the invention, the antibacterial capability and the fluorescence response capability of the coating are endowed by introducing 3, 4-diamino furoxan and 7-amino-4-methylcoumarin. The dihydroxyl group is introduced into the zwitterionic precursor by means of a free radical telomerization reaction. The introduction of polyurethane can improve the mechanical property of the coating, make up for the defect of mechanical property reduction caused by the introduction of the zwitterionic side chain, and provide excellent static antifouling capability for the coating.

Description

Organic silicon antifouling coating and preparation method thereof

Technical Field

The invention relates to a preparation method of a high-molecular antifouling coating, in particular to an organic silicon antifouling coating and a preparation method layer thereof, belonging to the technical field of marine fouling organism corrosion protection.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

Marine pollution means accumulation or adsorption of microorganisms and large organisms on the surface of marine facilities, various marine organisms are attached in the world, and the biological pollution can reduce the speed and maneuverability of ships, accelerate corrosion and increase fuel consumption; the adhesion of marine organisms can also damage the paint film, increasing the risk of mechanical failure of static structures such as buoys, piers and wharfs. Coating with tributyltin (TBT) has been the most effective way to combat marine fouling, but has been banned globally since 2008 due to its persistent toxicity to marine organisms.

The Si-O-Si main chain structure of the organic silicon endows the organic silicon with low surface energy and low elastic modulus, provides smaller adhesion strength for polluted organisms, and marine organisms can only be weakly adhered to the surface and can be removed through shearing force. In addition, the surface of the organic silicon coating is smooth, so that the resistance and oil consumption of the ship can be reduced. However, silicone coatings exhibit poor antifouling properties under static conditions and also have poor adhesion to the substrate, and therefore can suffer peeling or damage in use. Moreover, their crosslinked network structure is difficult to repair once damaged, which greatly limits their widespread use in the field of marine biofouling organism corrosion protection technology. CN112876984A discloses an environment-friendly marine antifouling coating and a preparation method thereof, coffee (such as nestle gold-brand instant pure coffee, and original Espresso instant pure coffee) is doped into organic silicon resin for curing and forming, which can effectively prevent adhesion of algae, prevent biofilm formation at the initial stage of marine biofouling, and has no pollution to the environment; CN111440519A discloses a mussel bionic-based amphiphilic antifouling coating and a preparation method thereof, wherein dopamine methacrylamide, mercapto polydimethylsiloxane, polyethylene glycol diacrylate, a photoinitiator and a solvent are mixed and coated on a substrate, and the mixture is cured under the irradiation of ultraviolet light, so that the problem of weak adhesion between a PDMS-based coating with low surface energy and the substrate is solved, protein pollution can be resisted, and the antifouling effect is realized. But none of the above coatings have self-healing capabilities.

At present, most researched marine antifouling coatings mainly comprise low-surface-energy antifouling coatings, surface microstructure bionic coatings, antifouling agent antifouling coatings and the like. However, in view of the defects that the static antifouling property of the low-surface-energy antifouling coating is poor, the surface structure of the surface microstructure bionic coating is easy to damage, and the bactericide antifouling coating can generate adverse effects on the environment, the application of the environment-friendly nano material to the antifouling coating is concerned by people.

Meanwhile, in order to facilitate overhauling and reduce accident risk, the monitoring of coating corrosion is paid more and more attention, and an organic silicon antifouling coating with fluorescent response is urgently needed.

On the other hand, a zwitterionic polymer (Polyzwitterion) is a polymer having both anionic and cationic groups on the macromolecular chain. Researches show that the zwitterionic polymer has excellent antifouling performance, and is closely related to a hydration layer on the surface of the zwitterionic polymer, and the tight hydration layer forms a physical and energy barrier so as to prevent the adsorption of microorganisms such as proteins and bacteria on the surface. The way of binding water on the surface of the zwitterionic polymer can be divided into two ways: hydrogen bonding water (hydrophilic material) and an ionic hydration layer (zwitterionic material). Polyethylene glycol (PEG) materials mainly combine water through hydrogen bonds, and research results show that one Ethylene Glycol (EG) unit can only combine 1 water molecule, one Sulfobetaine (SB) unit can tightly combine 7-8 water molecules, and one Methacryloyloxyethyl Phosphorylcholine (MPC) molecule can combine 15-25 water molecules, and the combination constant is higher than that of the EG unit. This indicates that the zwitterionic material can more tightly bind water molecules through ionic hydration, and the adsorption of microorganisms on the surface becomes more difficult due to the barrier formed by the hydrated layer, which is why the zwitterion has more excellent antifouling properties. However, zwitterionic polymers are readily swellable in aqueous solutions and thus have low mechanical properties and adhesion capabilities, which limits their use in marine antifouling coatings.

Polyurethane (PU) is a multi-block copolymer containing a large number of urethane groups in the molecular chain segment structure, and is composed of two different types of chain segments (soft and hard segments). The soft segments are composed of the soft segments of the oligomer polyol, and the hard segments are generally composed of the small molecule isocyanate and the chain extender. Due to the fact that a large number of polar groups (such as ester bonds, ether bonds and the like) exist on a molecular chain, intermolecular force and a large number of hydrogen bonds exist among the groups, and the combined action of the polar groups and the hydrogen bonds provides the polyurethane with a plurality of excellent performances, such as high mechanical strength, good chemical corrosion resistance, excellent adhesion and rubbing performance, and the polyurethane can be used in various complex environments, but the traditional polyurethane material does not have antifouling capacity.

Disclosure of Invention

In order to overcome the defects, the invention provides an organic silicon antifouling coating and a preparation method thereof, wherein the preparation method comprises the following steps: the coating comprises an organic silicon-oxime urethane self-repairing antifouling coating based on nano silver, an organic silicon antifouling coating with fluorescent response and an organic silicon polyurethane marine antifouling coating containing a zwitterion side chain.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

in a first aspect of the invention, a nano-silver based organosilicon-oxime urethane self-repairing antifouling coating is provided, and the structural formula of the coating material is as follows:

wherein n, x and y are natural numbers larger than zero.

The invention utilizes the nano silver (AgNPs) to improve the mechanical property of the coating on one hand and endow the coating with excellent antifouling property on the other hand. The specific principle is as follows: the mechanical strength of the coating is improved based on the reinforcing effect of AgNPs, meanwhile, the excellent sterilization performance of the AgNPs endows the coating with good antifouling performance, and the self-repairing performance of the coating is endowed by the synergistic effect of hydrogen bonds, disulfide bonds, metal coordination bonds and oxime carbamate bonds. The organic silicon-oxime urethane self-repairing antifouling coating based on nano silver is prepared by taking hydroxypropyl Polydimethylsiloxane (PDMS) at the double ends and Polytetrahydrofuran (PTMG) as main chains, Dimethylglyoxime (DMG) and 2-hydroxyethyl disulfide (TECH) as chain extenders, adding copper chloride to provide metal ion coordination, and finally adding a certain amount of AgNPs.

The invention also provides a preparation method of the organosilicon-oxime urethane self-repairing antifouling coating based on nano silver, which comprises the following steps:

uniformly mixing double-end hydroxypropyl polydimethylsiloxane, polytetrahydrofuran, isocyanate and a catalyst in an organic solvent, and reacting under the protection of inert gas to obtain an isocyanate-terminated prepolymer;

and (2) uniformly mixing the isocyanate-terminated prepolymer with 2-hydroxyethyl disulfide and dimethylglyoxime, reacting, adding copper chloride dihydrate for reacting after the reaction is finished, adding AgNPs for reacting after the reaction is finished, and removing the solvent to obtain the product.

In a second aspect of the invention, a silicone antifouling coating with a fluorescent response is provided, wherein the structural formula of the coating material is as follows:

wherein n and x are natural numbers larger than zero.

A large number of hydrogen bonds and metal coordination bonds are formed based on the combined action of the carbamate and the carbamido, so that the material has excellent mechanical strength, the adhesion force can be improved through the interaction of the hydrogen bonds with the substrate, and the antifouling agent introduced in a covalent bonding mode can continuously exert the antifouling capacity. The method comprises the steps of taking hydroxypropyl Polydimethylsiloxane (PDMS) at the two ends as a main body, taking 1, 4-Butanediol (BDO) as a chain extender, reacting with isophorone diisocyanate to synthesize a prepolymer terminated by isocyanate, introducing 3, 4-diamino furazane (DAF) and 7-amino-4-methyl coumarin (AMC) as antifouling groups, adding zinc chloride to provide metal ion coordination, and preparing the organic silicon marine antifouling coating with fluorescent response by utilizing the ultraviolet fluorescent response characteristic of the AMC.

The invention also provides a preparation method of the organic silicon antifouling coating with fluorescence response, which comprises the following steps:

uniformly mixing double-end hydroxypropyl polydimethylsiloxane, 1, 4-butanediol, isocyanate and a catalyst in an organic solvent, and reacting under the protection of inert gas to obtain an isocyanate-terminated prepolymer;

uniformly mixing the isocyanate-terminated prepolymer with 3, 4-diamino furoxan DAF and 7-amino-4-methylcoumarin AMC, continuing to react, and adding ZnCl after the reaction is finished ₂ And (4) continuing the reaction, and removing the solvent after the reaction is finished to obtain the catalyst. In a third aspect of the invention, a marine antifouling organosilicon polyurethane coating containing zwitter-ion side chains is provided, and the marine antifouling coatingThe structural formula of the coating material is as follows:

wherein n, x and p are natural numbers larger than zero.

The polyurethane modified organic silicon provides excellent adhesion and mechanical properties for the coating, and a hydration layer formed by the zwitterion side chain and water can provide good static antifouling capacity for the coating. Meanwhile, the fouling desorption performance of the organosilicon material is reserved. Hydroxypropyl-terminated polydimethylsiloxane as soft segment, IPDI as hard segment, 1, 4-butanediol (1,4-BD) and dihydric alcohol (PEDM (OH) containing zwitterionic precursor in side chain ₂ ) As chain extender, linear polymer with high molecular weight is obtained, Triethanolamine (TEOA) is added as a cross-linking agent to carry out cross-linking reaction to obtain a cross-linked network, and 1, 3-propane sultone (1,3-PS) and PEDM (OH) ₂ To obtain zwitterions. By controlling the chain extenders 1,4-BD and PDEM (OH) ₂ The content of zwitterions on the side chain of the polymer is adjusted according to the proportion, so that the mechanical property and the antifouling property of the coating are adjusted and controlled. At present, the preparation of the organic silicon marine antifouling coating with excellent mechanical property and static antifouling capacity is always considered to be a great challenge, and the organic silicon coating not only improves the mechanical property of the coating through the action of a cross-linking network and a hydrogen bond, but also endows the coating with excellent static antifouling capacity through a hydration layer formed by a zwitter-ion side chain and water.

The invention also provides a preparation method of the organic silicon polyurethane marine antifouling coating containing the zwitterion side chain, which comprises the following steps:

dissolving hydroxypropyl-terminated polydimethylsiloxane and IPDI in an organic solvent, and reacting under the protection of inert gas to obtain a prepolymer;

reacting said prepolymer with PDEM (OH) ₂ Reacting, adding 1,4-BD and 0.04g of dibutyltin dilaurate after the reaction is finished, continuing the reaction, adding TEOA after the reaction is finished, and reacting for 1 hour to obtain the polymerAn agent;

and (3) reacting the polymer with 1,3-PS at room temperature, and removing the solvent to obtain the polymer.

The invention has the beneficial effects that:

(1) the organosilicon-oxime urethane self-repairing antifouling coating based on nano-silver has the advantages of simple reaction conditions, good controllability and easier molecular structure design. The mechanical property of the material is improved by introducing AgNPs, the antifouling property is endowed to the material, and the antibacterial ability reaches 97.8%. Meanwhile, after AgNPs are introduced, the characteristics of low surface energy are not adversely affected, and the surface free energy is 20-22 mJ.m ^-2 And has good dirt release performance. The coating is endowed with self-repairing performance at room temperature by abundant hydrogen bonds, disulfide bonds, oxime urethane bonds and metal coordination bonds in the system.

(2) In the invention, after 3, 4-diamino furoxan and 7-amino-4-methylcoumarin are introduced into the organic silicon antifouling coating with fluorescent response, the organic silicon antifouling coating has no adverse effect on the characteristics of low surface energy of organic silicon and is only 24.86 mJ.m at most ^-2 (less than 30 mJ. m) ^-2 ) Has good dirt release performance. The hydrogen bond provided by the carbamido and carbamate structure of the invention ensures that the coating has good mechanical property and adhesion, and the metal coordination bond further enhances the mechanical strength. According to the invention, the antibacterial ability and the fluorescence response ability of the coating are endowed by introducing 3, 4-diamino furoxan and 7-amino-4-methylcoumarin, and based on the synergistic effect of the two, the antibacterial ability of the material reaches more than 99%.

(3) In the invention, the organic silicon polyurethane marine antifouling coating containing the zwitter-ion side chain adopts a simple method and introduces dihydroxyl into the zwitter-ion precursor by utilizing the free radical telomerization reaction. In the preparation process, the reaction of hydroxyl and isocyanate is fully utilized, and organic silicon and zwitterion are introduced into a polymer network in a covalent bond mode. The introduction of polyurethane can improve the mechanical property of the coating, make up for the defect of mechanical property reduction caused by the introduction of the zwitterionic side chain, and provide excellent static antifouling capability for the coating.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

Fig. 1 is an infrared spectrum of a nano-silver-based organosilicon-oxime urethane coating prepared in example 1 of the present invention.

FIG. 2 is a drawing of a nano-silver-based organosilicon-oxime urethane coating prepared in examples 1-4 of the present invention.

Fig. 3 is a self-repairing diagram of a nano-silver based silicone-oxime urethane coating prepared in the invention example 1.

FIG. 4 is a contact angle and surface free energy diagram of an organosilicon-oxime urethane coating based on nano-silver prepared in examples 1-4 of the invention.

FIG. 5 shows Scanning Electron Microscope (SEM) and X-ray energy spectrum (EDS) of a nano-silver-based organosilicon-oxime urethane coating prepared in examples 1-4 of the present invention.

FIG. 6 is an antibacterial performance diagram of an organosilicon-oxime urethane coating based on nano-silver prepared in embodiments 1-4 of the invention.

FIG. 7 is an infrared spectrum of a silicone antifouling coating with fluorescent response prepared in example 1 of the invention.

FIG. 8 is a drawing of the silicone antifouling coating with fluorescent response prepared in examples 1 to 4 of the present invention.

FIG. 9 is a graph of the contact angle and the surface free energy of the organic silicon antifouling coating with fluorescence response prepared in examples 1 to 4 of the invention.

FIG. 10 is a graph showing the adhesive strength of the organic silicon antifouling coatings with fluorescent response prepared in examples 1 to 4 of the present invention.

FIG. 11 is an antibacterial performance diagram of the organic silicon antifouling coating with fluorescence response prepared in examples 1 to 4 of the invention.

FIG. 12 is a stress-strain curve for coatings of different zwitterionic content.

FIG. 13 is a graph showing the bond strength of coatings with different zwitterionic contents on mild steel plates.

Figure 14 is a graph of simulated barnacle removal strength for different zwitterionic content coatings.

FIG. 15 is a graph of the number of marine bacterial colonies adhered to coatings of varying zwitterionic content.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

An organosilicon-oxime urethane self-repairing antifouling coating based on nano-silver has a structural formula as follows:

in the formula (I), n is a natural number larger than zero.

According to the present invention, in formula (i), n is preferably 6 to 18.

According to the invention, a preparation method of the organosilicon-oxime urethane self-repairing antifouling coating based on nano silver, a preferred embodiment, comprises the following steps:

10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 2000), 1.0g of polytetrahydrofuran (Mn: 1000) and 2.66g of isophorone diisocyanate are added into a three-neck flask provided with a mechanical stirring paddle, a nitrogen circulating system and a condensing system, 0.1g of dibutyltin dilaurate is added as a catalyst, tetrahydrofuran is used as a solvent, and after complete dissolution, the reaction is carried out at 65 ℃ for 3 hours under the protection of nitrogen, so as to obtain the isocyanate-terminated prepolymer. Then adding 0.3g of 2-hydroxyethyl disulfide and 0.46g of dimethylglyoxime, continuously reacting for 3.0h, adding 0.18g of copper chloride dihydrate, continuously stirring for 2h, finally adding 0.9g of AgNPs, continuously stirring for 3.0h, and evaporating the solvent to obtain the organic silicon-oxime urethane antifouling self-repairing coating based on nano silver.

According to the invention, the addition amount of Polytetrahydrofuran (PTMG) is preferably 5-20% of the mass of the double-end hydroxypropyl polydimethylsiloxane.

In some embodiments, the 2-hydroxyethyl disulfide is added in an amount of 20 to 60% by mole based on the amount of hydroxypropyl dimethicone.

In some embodiments, the dimethylglyoxime is added in an amount of 50 to 150% by mole based on the amount of hydroxypropyl dimethicone at the terminal end.

In some embodiments, the prepolymer is reacted at a temperature of 50 to 70 ℃, most preferably 65 ℃ for 1 to 4 hours.

In some embodiments, the metal to ligand molar ratio (Cu) ²⁺ : DMG) is maintained at 1 (2-4).

In some embodiments, AgNPs is added in an amount of 3% to 9% of the hydroxypropyl dimethicone at the terminal end.

In some embodiments, AgNPs are vigorously stirred for 2-5 hours after addition.

In some embodiments, the solvent is tetrahydrofuran.

In some embodiments, the hydroxypropyl-terminated polydimethylsiloxane has a relative molecular weight of 1000 to 3000

In some embodiments, the mole ratio of hydroxypropyl-terminated polydimethylsiloxane to isophorone diisocyanate is 1: (1.5-4), and more preferably 1: 2.4.

in some embodiments, dibutyltin dilaurate is added in an amount of 0.5 wt% based on the total mass of the hydroxypropyl dimethicone.

According to the invention, the organosilicon-oxime urethane self-repairing coating based on nano-silver is used as an antifouling coating.

According to the invention, the marine antifouling coating is the organosilicon-oxime urethane polymer material based on nano-silver.

The principle of the invention is as follows:

according to the invention, double-end hydroxypropyl Polydimethylsiloxane (PDMS) and polytetrahydrofuran (molecular weight is 1000) are used as main chains, Dimethylglyoxime (DMG) and 2-hydroxyethyl disulfide (TECH) are used as chain extenders, copper chloride is added to provide metal ion coordination, and finally a certain amount of AgNPs is added to prepare the organosilicon-oxime urethane polymer material based on nano silver, which can be used as a marine antifouling coating. The AgNPs endow the coating with good mechanical strength and antifouling performance. The synergistic effect of hydrogen bond, disulfide bond, metal coordination bond and oxime urethane bond provides self-repairing performance of the coating. The PDMS based coatings also have low surface energy characteristics.

The organic silicon antifouling coating with fluorescence response has the following structural formula:

in the formula (II), n is a natural number larger than zero.

According to the present invention, n is preferably 6 to 20 in formula (ii).

According to the present invention, a preferred embodiment of the method for preparing a silicone antifouling coating having a fluorescent response comprises the steps of:

10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 2000), 0.45g of 1, 4-butanediol and 2.93g of isophorone diisocyanate are added into a three-neck flask provided with a mechanical stirring paddle, a nitrogen circulating system and a condensing system, 0.06g of dibutyltin dilaurate is added as a catalyst, tetrahydrofuran is used as a solvent, and after complete dissolution, the reaction is carried out at 70 ℃ for 1.0h under the protection of nitrogen, so as to obtain the isocyanate-terminated prepolymer.

Then 0.3g of 3, 4-Diaminofuroxan (DAF) and 0.03g of 7-amino-4-methylcoumarin (AMC) were added, the reaction was continued for 3.0h, and finally 0.136g of ZnCl was added ₂ And continuously stirring for 1.0h to obtain colorless liquid, and evaporating the solvent to obtain the organic silicon antifouling coating with fluorescent response.

In some embodiments, the 1, 4-butanediol is added in an amount of 80 to 120% by mole based on the amount of hydroxypropyl dimethicone at the terminal end;

in some embodiments, 7-amino-4-methylcoumarin (AMC) is added in an amount of 0.02g to 0.04 g.

In some embodiments, the reaction temperature is 60-90 ℃ and the reaction time is 1-4 h.

In some embodiments, the metal to ligand molar ratio (Zn) ²⁺ : DAF) is maintained at 1 (2 to 4)

In some embodiments, the solvent is tetrahydrofuran.

In some embodiments, the reaction temperature is 60 to 90 ℃, most preferably 70 ℃.

In some embodiments, the isocyanate-terminated prepolymer is prepared as follows:

mixing double-end hydroxypropyl polydimethylsiloxane, 1, 4-butanediol and isophorone diisocyanate, adding dibutyltin dilaurate as a catalyst and tetrahydrofuran as a solvent, heating to 60-90 ℃ under the protection of nitrogen, and reacting to obtain the isocyanate-terminated prepolymer.

In some embodiments, the mole ratio of hydroxypropyl-terminated polydimethylsiloxane to isophorone diisocyanate is 1: (1-5), more preferably 1: 5.

in some embodiments, dibutyltin dilaurate is added in an amount of 0.5 wt% based on the total mass of the isocyanate-terminated prepolymer.

According to the invention, the use of the above-described silicone polymers having a fluorescent response as coating materials.

According to the invention, the marine antifouling coating is the organic silicon polymer with the fluorescence response.

The principle of the invention is as follows:

according to the invention, a double-end hydroxypropyl Polydimethylsiloxane (PDMS) main body material, 1, 4-Butanediol (BDO) and 3, 4-diamino furo (DAF) are used as chain extenders, and 7-amino-4-methylcoumarin (AMC) is used as a capping reagent, so that the organic silicon antifouling coating with fluorescent response is prepared. The active part of 1,2, 5-oxadiazole heterocycle and AMC benzopyrone ring structure in DAF have bactericidal ability, AMC has ultraviolet fluorescence response characteristic, and high-efficiency antibacterial and fluorescence response ability is provided for the coating. A large number of hydrogen bonds are formed in a system due to the existence of the carbamate group and the urea group, the zinc ions and the DAF can form coordinate bonds, and the good mechanical property and the self-repairing capability are endowed to the coating through the combined action of the hydrogen bonds and the coordinate bonds.

A dihydroxy-terminated zwitterionic precursor is introduced into an organosilicon polyurethane coating as a side chain.

A dihydroxy-terminated zwitterionic precursor having the structure:

among these, p is 7 to 15, and p is 10.

According to the invention, the preparation method of the dihydroxyl-terminated zwitterionic precursor comprises the following steps:

mixing dimethylaminoethyl methacrylate (DEM), 3-mercapto-1, 2-propylene glycol (TPG) and an initiator in Tetrahydrofuran (THF), adding into a flask, bubbling for 30 minutes with nitrogen, reacting for 10-20 hours at 60-80 ℃ under the condition of nitrogen, removing excessive solvent by reduced pressure distillation after the reaction is finished, precipitating the product in n-hexane, and putting the product in a vacuum drying oven at 50 ℃ for 48 hours to obtain the catalyst.

In some embodiments, the DEM to TPG ratio is 5:1,10: 1,20: 1, more preferably 10: 1.

in some embodiments, the initiator is Azobisisobutyronitrile (AIBN).

In some embodiments, the initiator is used in an amount of 0.1% to 0.3% of the total mass of the DEM.

In some embodiments, the solvent is THF.

In some embodiments, the reaction temperature is 60-80 ℃, most preferably 70 ℃.

According to the present invention, the method for preparing the dihydroxy-terminated zwitterionic precursor comprises the following steps: DEM and TPG are mixed according to the proportion of 10:1 mol ratio of AIBN is 0.15 percent of the mass of DEM, tetrahydrofuran is used as a solvent to control the monomer concentration to be about 20 percent, the raw materials and the solvent are added into the three-neck flask, then nitrogen is used for bubbling for 30 minutes to remove dissolved oxygen in the solution, and then the temperature is raised to 70 ℃ for reaction for 12 hours. And after the reaction is finished, removing most of the solvent by using a rotary evaporator, precipitating the product in n-hexane, collecting the precipitate, and transferring the precipitate into a vacuum drying oven at 50 ℃ for drying for 48 hours to obtain the compound.

According to the present invention, the dihydroxy-terminated zwitterionic precursor described above is incorporated as a modifying group into a silicone polyurethane coating.

According to the invention, zwitterions are introduced into the side chains to carry out hydrophilic modification on the organic silicon polyurethane coating, and the static antifouling capability of the organic silicon polyurethane coating is improved by combining the static action of the zwitterions with water molecules. The invention selects sulfo zwitterions with strong hydrophilicity and stable chemical property, and prepares the organic silicon polyurethane antifouling coating with the side chain containing zwitterions by a chemical grafting method. The experimental result shows that the prepared coating not only retains the specific dynamic antifouling capacity (the removal force of the simulated barnacles is less than 0.5MPa) of the organic silicon coating, but also improves the anti-adhesion capacity to marine bacteria (the maximum antibacterial efficiency is 96%).

According to the present invention, there is also provided a silicone polyurethane polymer having a zwitterionic in a side chain, having a structure represented by formula (iii):

in the formula (III), n, x and p are natural numbers larger than zero.

In some embodiments, in formula (iii), p-7-15, x-8-12, and n-7-20.

According to the invention, the preparation method of the organic silicon polyurethane containing the zwitterion side chain comprises the following steps:

hydroxypropyl-terminated polydimethylsiloxane is used as a soft segment, IPDI is used as a hard segment, PDEM (OH)2 and 1,4-BD are used as chain extenders, TEOA is used as a cross-linking agent, and finally, under the action of 1,3-PS, a ring opening reaction is carried out to prepare a target product.

In some embodiments, the zwitterion is added in an amount of 0%, 5%, 10%, 14% of the total mass.

In some embodiments, the reaction temperature is 60-80 ℃ and the reaction time is 30 hours.

In some embodiments, the hydroxypropyl dimethicone has a relative molecular weight of 2000.

In some embodiments, the mole ratio of hydroxypropyl polydimethylsiloxane to isophorone diisocyanate is 1: : (2-4), further preferably 1: 3.

a preferred embodiment of the process for preparing a zwitterionic side-chain containing silicone polyurethane according to the present invention comprises the steps of:

10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g IPDI were dissolved in a quantity of tetrahydrofuran and added to a three-necked flask equipped with reflux condensation and mechanical stirring, placed in a 70 ℃ oil bath under nitrogen blanket for 1h to give a prepolymer, and then 0.43g PDEM (OH) was added to the three-necked flask ₂ After the reaction for 1 hour, 0.74g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to a three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of TEOA was added to the flask, and the reaction was continued for 1 hour. And cooling the polymer to room temperature, adding 0.36g of 1,3-PS into the three-neck flask, reacting for 24 hours at room temperature, and volatilizing the solvent to obtain the high-performance high-temperature-resistant high-performance high-temperature-resistant high-performance liquid crystal.

The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.

A first part: organosilicon-oxime urethane self-repairing antifouling coating based on nano-silver

Example 1

10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 2000), 1.0g of polytetrahydrofuran (Mn: 1000) and 2.66g of isophorone diisocyanate are added into a three-neck flask provided with a mechanical stirring paddle, a nitrogen circulating system and a condensing system, 0.05g of dibutyltin dilaurate is added as a catalyst, tetrahydrofuran is used as a solvent, and after complete dissolution, the reaction is carried out at 65 ℃ for 3 hours under the protection of nitrogen, so as to obtain the isocyanate-terminated prepolymer. Then adding 0.3g of 2-hydroxyethyl disulfide and 0.46g of dimethylglyoxime, continuously reacting for 3 hours, adding 0.18g of copper chloride dihydrate, continuously stirring for 2 hours, finally adding 0.9g of AgNPs, continuously stirring for 3 hours, and evaporating the solvent to obtain the organic silicon-oxime urethane self-repairing antifouling coating based on nano-silver.

Example 2

As described in example 1, except that AgNPs was 0.6 g.

Example 3

As described in example 1, except that AgNPs was 0.3 g.

Example 4

As described in example 1, except that AgNPs was 0.0 g.

Example 5

As described in example 1, except that the amount of 2-hydroxyethyl disulfide added was 0.15g, the amount of isophorone diisocyanate added was 2.44 g.

Example 6

The procedure is as described in example 1, except that 0.45g of 2-hydroxyethyl disulfide and 2.88g of isophorone diisocyanate are added.

Example 7

As described in example 1, except that the amount of dimethylglyoxime added was 0.29g and the amount of isophorone diisocyanate added was 1.92 g.

Example 8

As described in example 1, except that the amount of dimethylglyoxime added was 0.58g and the amount of isophorone diisocyanate added was 2.81 g.

Example 9

As described in example 1, except that the amount of dimethylglyoxime added was 0.87g and the amount of isophorone diisocyanate added was 3.03 g.

Example 10

Except that the isocyanate terminated prepolymer was prepared at 50 ℃ for 4.0 hours as described in example 1.

Example 11

Except that the isocyanate terminated prepolymer was prepared at 60 ℃ for 3.5 hours as described in example 1.

Example 12

Except that, as described in example 1, when a coordination bond is formed by adding a metal ion, CuCl ₂ The amount added was 0.272 g.

Example 13

Except that, as described in example 1, when a coordination bond is formed by adding a metal ion, CuCl ₂ The amount added was 0.136 g.

Example 14

The procedure is as described in example 1, except that 0.5g of polytetrahydrofuran and 2.54g of isophorone diisocyanate are added.

Example 15

The procedure was as described in example 1, except that 2.0g of polytetrahydrofuran was added and 2.88g of isophorone diisocyanate was added.

Example 16

The procedure was as in example 1 except that AgNPs were added and stirred for 2 h.

Example 17

Except that AgNPs was added and stirred for 5h as described in example 1.

Comparative example 1

To better illustrate the effect of hydroxypropyl-terminated polydimethylsiloxane on the material, we chose different molecular weight hydroxypropyl-terminated polydimethylsiloxanes in the comparative examples. 10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 1000), 1.0g of polytetrahydrofuran (Mn: 1000) and 3.7g of isophorone diisocyanate are added into a three-neck flask provided with a mechanical stirring paddle, a nitrogen circulating system and a condensing system, 0.1g of dibutyltin dilaurate is added as a catalyst, tetrahydrofuran is used as a solvent, and after complete dissolution, the reaction is carried out at 65 ℃ for 3 hours under the protection of nitrogen, so as to obtain the isocyanate-terminated prepolymer. Then adding 0.3g of 2-hydroxyethyl disulfide and 0.46g of dimethylglyoxime, continuing to react for 3 hours, adding 0.18g of copper chloride dihydrate, continuing to stir for 2 hours, finally adding 0.9g of AgNPs, violently continuing to stir for 3 hours, and evaporating the solvent to obtain the nano-silver-based organic silicon-oxime urethane self-repairing coating polymer.

Comparative example 2

As in comparative example 1, except that hydroxypropyl-terminated polydimethylsiloxane (Mn: 3000) and isophorone diisocyanate were added in an amount of 2.28 g.

Test example 1

An infrared spectrum of one of the nano-silver based organosilicon-oxime urethane coatings obtained in example 1 was tested and shown in fig. 1. 3320cm ^-1 Is the stretching vibration of-NH bond in carbamate (-NH-CO-O-). Peak value range is 2950cm ^-1 Corresponding to-CH stretching vibration. The peak at 1700cm-1 is attributed to C ═ O. 1660cm ^-1 The successful introduction of Dimethylglyoxime (DMG) can be demonstrated by tensile vibration at C ═ N. The peak of the Si-O-Si structure appears at 1090cm ^-1 And 1022cm ^-1 To (3). These indicate the success of the synthesis of the nanosilver-based silicone-oxime urethane coating.

The tensile patterns of one of the nanosilver-based organosilicon-oxime urethane coatings prepared in test examples 1-4 are shown in figure 2. For the sample without AgNPs filler, the elongation at break is around 630% while the tensile strength is 0.6MPa, which indicates that the sample itself has a certain tensile strength even without reinforcement by the nanofiller, which is attributed to the action of hydrogen bonds and metal coordination bonds in the system. As the AgNPs addition amount increases, the elongation at break decreases, but the tensile strength increases significantly. When the AgNPs content is increased from 3 wt% to 9 wt%, the tensile strength rises from 0.6MPa to 2.75 MPa. This is because the system includes, in addition to the effects of hydrogen bonding and metal coordination bonding, the reinforcing effect of the nanofiller.

The self-repair graph of the nano-silver based silicone-oxime urethane coating prepared in example 1 is tested and shown in fig. 3. Based on disulfide bonds, oxime-urethane bonds, metal coordination bonds and hydrogen bonds contained in a system, the material has self-repairing capability even at room temperature. We cut the dumbbell from the middle and then align the two sections and after 12h at room temperature the fracture almost completely disappeared. Fig. 3 shows the tensile curve before and after self-healing. The healing efficiency can reach 91.7% through calculation.

A graph of contact angle and surface free energy of one of the nano-silver based organosilicon-oxime urethane coatings prepared in examples 1-4 was tested, as shown in fig. 4. As AgNPs have hydrophobicity, the contact angle of water is gradually increased with the increase of the content of the AgNPs, and the maximum contact angle reaches 104.82 degrees. The surface free energy of the coating is 20.03-22.45 mJ.m ^-2 And therefore, the AgNPs content is not considered to have a direct influence on the surface energy of the coating. The research shows that when the surface energy is less than 25 mJ.m ^-2 And the composition has good dirt release performance, and has a remarkable inhibiting effect on adhesion of mussels, barnacles and other marine organisms.

Test examples 1-4 Scanning Electron Microscopy (SEM) and X-ray spectroscopy (EDS) profiles of one of the nanosilver-based organosilicon-oxime urethane coatings prepared are shown in fig. 5. The surface morphology was tested by Scanning Electron Microscopy (SEM) at 1000 times. We can see the tiny protrusions on the surface because of the microphase separation caused by the thermodynamic incompatibility of the hard segment and the soft segment in the system, and the microphase separation structure is also an important factor for improving the mechanical properties. And the surface element distribution is explored through energy dispersive X-ray spectroscopy (EDS), the distribution situation of C, S, Si, Cu and Ag on the surface is clearly seen, copper ions and silver nanoparticles are not agglomerated, and the Cu ions and the silver nanoparticles are also shown to be agglomerated ²⁺ Successfully forms metal coordination bonds with DMG and uniformly disperses AgNPs.

The antibacterial performance of one of the nano-silver based organosilicon-oxime urethane coatings prepared in examples 1-4 was tested and shown in fig. 6. Blank samples as controls had a high density of bacterial adhesion. However, the colony density of the coating surface without AgNPs is still high, the colony number is obviously reduced along with the gradual increase of the addition amount of AgNPs, and only a very small amount of colonies exist on the coating surface with the addition amount of AgNPs of 9%. And calculating the antibacterial efficiency to obtain that the antibacterial capacity of the coating without AgNPs only reaches 20 percent. This is because Cu as a coordinated metal ²⁺ Plays a certain role in bacteriostasis, butDue to Cu ²⁺ The content of (a) is low, so that the antibacterial effect is not remarkable. With the increase of AgNPs content, the bacteriostatic efficiency is gradually increased to reach 97.8 percent at most.

A second part: silicone antifouling coating with fluorescent response

Example 18

10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 2000) and 0.45g of 1, 4-butanediol and 2.93g of isophorone diisocyanate were charged into a 250ml three-necked flask equipped with a mechanical stirring blade, a nitrogen circulation system and a condensation system. Dibutyltin dilaurate was added as a catalyst in an amount of 0.5% of the total mass of the isocyanate-terminated prepolymer. Tetrahydrofuran is used as a solvent, after the tetrahydrofuran is completely dissolved, the temperature is raised to 70 ℃ under the protection of nitrogen, and the reaction lasts for 2.5 hours, so that the isocyanate-terminated prepolymer is obtained. Then 0.3g of 3, 4-diamino furoxan is added as an antifouling group and is further subjected to chain extension to react for 2.0h, then 7-amino-4-methylcoumarin is added as another antifouling group and is used as an end capping agent to continue to react for 2.5h, and finally 0.136g of ZnCl is added ₂ Stirring for 2.0h to obtain Zn ²⁺ Forming a coordinate bond with 3, 4-diamino furoxan, and evaporating the solvent to obtain the organic silicon antifouling coating with fluorescent response.

Example 19

As described in example 1, except that:

the amount of 3, 4-diaminofurazane added was 0.2g, and the amount of isophorone diisocyanate added was 2.7 g.

Example 20

As described in example 1, except that:

the amount of 3, 4-diaminofurazane added was 0.1g, and the amount of isophorone diisocyanate added was 2.5 g.

Example 21

As described in example 1, except that:

the amount of 3, 4-diaminofurazane added was 0.0g, and the amount of isophorone diisocyanate added was 2.26 g.

Example 22

As described in example 1, except that:

the amount of 1, 4-butanediol added was 0.36g, and the amount of isophorone diisocyanate added was 2.7 g.

Example 23

As described in example 1, except that:

the amount of 1, 4-butanediol added was 0.54g, and the amount of isophorone diisocyanate added was 3.14g

Example 24

As described in example 1, except that:

the amount of 7-amino-4-methylcoumarin (AMC) added was 0.02g

Example 25

As described in example 1, except that:

the amount of 7-amino-4-methylcoumarin (AMC) added was 0.04g

Example 26

As described in example 1, except that:

in the preparation process of the isocyanate-terminated prepolymer, the reaction temperature is 90 ℃ and the reaction time is 1.0 h.

Example 27

As described in example 1, except that:

in the preparation process of the isocyanate-terminated prepolymer, the reaction temperature is 60 ℃ and the reaction time is 4.0 h.

Example 28

As described in example 1, except that:

in the preparation process of the isocyanate-terminated prepolymer, the reaction temperature is 80 ℃ and the reaction time is 2.0 h.

Example 29

As described in example 1, except that:

ZnCl upon addition of metal ions to build coordination bonds ₂ The amount added was 0.204 g.

Example 30

As described in example 1, except that:

ZnCl upon addition of metal ions to build coordination bonds ₂ The amount added was 0.102 g.

Comparative example 3

To be betterTo illustrate the effect of hydroxypropyl-terminated polydimethylsiloxanes on the material, in the comparative example we selected different molecular weight hydroxypropyl-terminated polydimethylsiloxanes. 10g of double-ended hydroxypropyl polydimethylsiloxane (Mn: 1000) and 0.45g of 1, 4-butanediol and 4.27g of isophorone diisocyanate were charged into a 250ml three-necked flask equipped with a mechanical stirring blade, a nitrogen circulation system and a condensation system. Dibutyltin dilaurate was added as a catalyst in an amount of 0.5% of the total mass of the isocyanate-terminated prepolymer. Tetrahydrofuran is used as a solvent, after the tetrahydrofuran is completely dissolved, the temperature is raised to 70 ℃ under the protection of nitrogen, and the reaction lasts for 2.5 hours, so that the isocyanate-terminated prepolymer is obtained. Then 0.4g of 3, 4-diamino furoxan is added as an antifouling group and is subjected to chain extension for 2 hours, then 7-amino-4-methylcoumarin is added as another antifouling group and is used as a blocking agent, the reaction is continued for 2.5 hours, and finally 0.136g of ZnCl is added ₂ Stirring for 2h to obtain Zn ²⁺ Forming a coordinate bond with the 3, 4-diamino-furoxan, and evaporating the solvent to obtain the organosilicon polymer with efficient antibacterial and fluorescent response.

Comparative example 4

As in comparative example 1, except that:

the relative molecular mass of the double-end hydroxypropyl polydimethylsiloxane was 3000, and the amount of added isophorone diisocyanate was 2.79 g.

Test example 2

The infrared spectrum of the silicone antifouling coating having a fluorescent response obtained in example 18 was tested and shown in fig. 7. From FIG. 7, the peak was 3350cm ^-1 Assigned to the tensile vibration of the-NH bond in the carbamate (-NH-CO-O-). Peak value range is 2980cm ^-1 Corresponding to-CH stretching vibrations (asymmetric and symmetric vibrations). 2270cm ^-1 The disappearance of the characteristic peak at (a) demonstrates the occurrence of the reaction of isocyanate with hydroxyl groups. 1660cm ^-1 The successful incorporation of 3, 4-diaminofuroxan can be demonstrated by tensile vibration corresponding to 3, 4-diaminofuroxan-C ═ N. The peak of the-Si-O-Si-structure appeared at 1130cm ^-1 And 1048cm ^-1 To (3). These indicate that the synthesis of PDMS-DAF-x-AMC was successful.

Test examples 18 to 21 all the compounds prepared in examples 18 to 21 were found to have fluorescenceThe tensile profile of the responsive silicone anti-fouling coating is shown in fig. 8. As can be seen from FIG. 8, PDMS-DAF-0.0-AMC has the largest strain value, and the elongation at break can reach more than 1000%, but the stress is low and the tensile strength is only 0.3 MPa. This is probably because the mechanical strength is lower due to the lower content of hard segments in the system and the small number of hydrogen bonds. However, as the amount of DAF added increases, the stress increases significantly, wherein the tensile strength of PDMS-DAF-0.3-AMC reaches 2.78MPa, and the elongation at break reaches 590%. PDMS-DAF-0.3-AMC has the optimal mechanical property. This is attributed to the fact that as the content of DAF increases, more and more polyurea structures are formed in the system, which can enrich the hydrogen bonds in the system and additionally via Zn ²⁺ The coordination of (2) further improves the mechanical property.

The contact angle and surface free energy graphs of the organic silicon antifouling coating with fluorescence response prepared in the examples 18-21 are tested, and are shown in FIG. 9. As can be seen from FIG. 9, the PDMS-DAF-x-AMC coating exhibited a hydrophobic surface due to the hydrophobicity of the polysiloxane, and the water contact angle of PDMS-DAF-0.3-AMC reached a maximum of 105.84 DEG, showing good hydrophobicity, with increasing hydrophobicity. The surface free energy of the PDMS-DAF-x-AMC coating is 21.11-24.86 mJ.m ^-2 In the meantime. The research shows that when the surface energy is lower than 30 mJ.m ^-2 It can inhibit adhesion of mussel, barnacle and other marine organisms, and is less than 25 mJ.m ^-2 And the surface energy pair of PDMS-Pu-Tx percent accords with the optimal theoretical range of marine organism fouling release.

The adhesive strength performance graphs of the high-efficiency antibacterial and fluorescence-responsive organic silicon coatings prepared in examples 18-21 are shown in fig. 10. FIG. 10 shows the adhesion between the PDMS-DAF-x-AMC coating and the glass and tinplate. Based on the hydrogen bond interaction between the PDMS-DAF-x-AMC coating and the surface of the base material, the coating has excellent adhesion strength with the surface of the base material. The result shows that the adhesion with the glass slide can reach 1.5MPa to the maximum and 1.03MPa to the minimum, in addition, the adhesion of the coating on the tin plate is larger than that of the coating on the glass, the adhesion can reach 2.0MPa to the maximum and 1.36MPa to the minimum. This is due to the fact that sandpaper finished tinplate surfaces are rough and can interact with the coating by mechanical interlocking, thereby further enhancing adhesion. As the adhesion of the PDMS-DAF-x-AMC coating to the substrate is related to hydrogen bonds, the adhesion of the coating is gradually enhanced with the increase of the content of the DAF.

The antibacterial performance graphs of the organic silicon antifouling coatings with fluorescence responses prepared in the test examples 18-21 are shown in FIG. 11. The control coating sample had a high density of bacterial adhesion. However, the number of colonies on the surface of PDMS-DAF-0.0-AMC coating without 3, 4-diamino furazane (DAF) was significantly reduced because 7-amino-4-methylcoumarin (AMC) has a benzopyrone ring structure with bactericidal activity, but the bacteriostatic activity reached only 78% due to the lower AMC content. As the DAF content increased, the bacteriostatic efficiency of PDMS-DAF-0.1-AMC reached 90%, and only a few colonies were found on the coatings of PDMS-DAF-0.2-AMC and PDMS-DAF-0.3-AMC. The bacteriostasis efficiency reaches more than 99 percent. The results show that PDMS-DAF-x-AMC has excellent antibacterial ability based on the synergistic effect of 3, 4-diamino furoxan (DAF) and 7-amino-4-methylcoumarin (AMC).

And a third part: organic silicon polyurethane marine antifouling coating containing zwitter-ion side chain

Example 31: dissolving DEM and TPG in a certain amount of tetrahydrofuran according to the ratio of 5:1, adding the DEM and TPG into a three-neck flask, adding 0.15 wt% of AIBN, bubbling nitrogen for 30 minutes, sealing the three-neck flask, putting the three-neck flask into an oil bath at the temperature of 60-80 ℃, and stirring for reacting for 12-14 hours to obtain PDEM (OH) ₂ 。

Example 32: dissolving DEM and TPG in a certain amount of tetrahydrofuran according to the ratio of 10:1, adding the DEM and TPG into a three-neck flask, adding 0.15 wt% of AIBN, bubbling nitrogen for 30 minutes, sealing the three-neck flask, putting the three-neck flask into an oil bath at the temperature of 60-80 ℃, and stirring for reacting for 12-14 hours to obtain PDEM (OH) ₂ 。

Example 33: DEM and TPG are dissolved in a certain amount of tetrahydrofuran according to the ratio of 20:1, added into a three-neck flask, added with 0.15 wt% of AIBN, bubbled with nitrogen for 30 minutes, sealed, put into an oil bath at 60-80 ℃, stirred and reacted for 12-14 hours to obtain PDEM (OH) ₂ 。

Example 34: 10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g of ipdi were dissolved in a certain amount of tetrahydrofuran and added to a three-necked flask equipped with reflux condensation and mechanical stirring, placed in an oil bath at 60-80 ℃ under nitrogen protection and reacted for 1h to obtain a prepolymer, then 0.76g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to the three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of teoa was added to the flask and the reaction was continued for 1 hour to obtain a polymer coating PDMS-zPDEM-0.

Example 35: 10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g IPDI were dissolved in a quantity of tetrahydrofuran and added to a three-necked flask equipped with reflux condensation and mechanical stirring, placed in an oil bath at 60-80 ℃ under nitrogen blanket for 1h to give a prepolymer, and then 0.43g PDEM (OH) was added to the three-necked flask ₂ After the reaction for 1 hour, 0.74g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to a three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of TEOA was added to the flask, and the reaction was continued for 1 hour. The polymer was cooled to room temperature, and 0.36g of 1,3-PS was added to the three-necked flask and reacted at room temperature for 24 hours to obtain a polymer coating PDMS-zPDEM-5.

Example 36: 10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g IPDI were dissolved in a quantity of tetrahydrofuran and added to a three-necked flask equipped with reflux condensation and mechanical stirring, placed in an oil bath at 60-80 ℃ under nitrogen blanket for 1h to give a prepolymer, and then 0.88g PDEM (OH) was added to the three-necked flask ₂ After the reaction for 1 hour, 0.72g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to a three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of TEOA was added to the flask, and the reaction was continued for 1 hour. The polymer was cooled to room temperature, and 0.73g of 1,3-PS was added to the three-necked flask and reacted at room temperature for 24 hours to obtain a polymer coating PDMS-zPDEM-10.

Example 37: 10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g of IPDI were dissolved in a quantity of tetrahydrofuran and added to the contentsIn a three-neck flask with reflux condensation and mechanical stirring, the mixture was put into an oil bath at 60-80 ℃ under nitrogen protection for reaction for 1 hour to obtain a prepolymer, and then 1.31g of PDEM (OH) was added into the three-neck flask ₂ After the reaction for 1 hour, 0.70g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to a three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of TEOA was added to the flask, and the reaction was continued for 1 hour. The polymer was cooled to room temperature, and 1.08g of 1,3-PS was added to the three-necked flask and reacted at room temperature for 24 hours to obtain a polymer coating PDMS-zPDEM-14.

Comparative example 5: the coating is used

184, purchased from dow corning company, consisting of a first component and a second component, wherein the first component and the second component are mixed for use in a mass ratio of 10: 1. The component A mainly comprises vinyl-terminated polydimethylsiloxane, vinyl resin and polydimethylsiloxane-polymethylhydrosiloxane copolymer, the component B mainly comprises a mixture containing a platinum catalyst, and the coating is named as PDMS.

Comparative example 6: 10g of hydroxypropyl-terminated polydimethylsiloxane (M) _n 2000g/mol) and 3.67g IPDI were dissolved in a quantity of tetrahydrofuran and added to a three-necked flask equipped with reflux condensation and mechanical stirring, placed in an oil bath at 60-80 ℃ under nitrogen blanket for 1h to give a prepolymer, and then 1.31g PDEM (OH) was added to the three-necked flask ₂ After 1 hour of reaction, 0.70g of 1,4-BD and 0.04g of dibutyltin dilaurate were added to the three-necked flask, and the reaction was continued for 3 hours, and finally 0.15g of TEOA was added to the flask and the reaction was continued for 1 hour to obtain a polymer coating PDMS-PDEM-14.

As shown in FIG. 12, example 34 had good strength and flexibility, a tensile strength of 8.28MPa and an elongation at break of 2061%. Compared with example 34, example 37 introduces side chains of macromolecules, the tensile strength is 2.11MPa, and the elongation at break is 754%, which is probably because the introduction of the side chains destroys the hydrogen bonding interaction between polymer chains, which indicates that the introduction of the side chains of macromolecules can reduce the mechanical properties of the material. In example 37, compared with comparative example 6, the zwitterion is generated in the side chain, and the tensile strength and the elongation at break are improved, probably because the electrostatic interaction between the zwitterions plays a role in crosslinking, which shows that the existence of the side chain zwitterion can compensate the problem of the reduction of the mechanical property caused by the introduction of the side chain to a certain extent. Overall, as the content of the zwitterionic side chain increases, the tensile strength of the polymer decreases (7.59 MPa for example 35, 6.73MPa for example 36, and 6.07MPa for example 37), and the elongation at break also decreases (2379% for example 35, 2035% for example 36, and 1203% for example 37), and even though the introduction of the zwitterionic segment decreases the mechanical properties of the material, the material still has high mechanical properties.

As shown in fig. 13, the bond strength of example 34 is greatest and gradually decreases with increasing zwitterionic side chains, probably because the introduction of side chains decreases the hydrogen bond density between the coating and the polar groups of the substrate. In general, the bond strengths of examples 34, 35, 36, and 37 were all greater than 1.0MPa (2.4-3.3MPa), indicating that they are sufficient for marine antifouling coating applications. In contrast, comparative example 5 is weak in adhesive strength (0.3MPa) because its nonpolar structure makes it easy to separate from the substrate.

As shown in fig. 14, comparative example 5 has the lowest fouling desorption performance, only around 0.2MPa, because the low surface energy and low elastic modulus properties of polysiloxane impart excellent fouling desorption performance to its coating. The removal force of the simulated barnacles of example 34, example 35, example 36 and example 37 is in the range of 0.3-0.5MPa, slightly higher than that of comparative example 5, but much smaller than that of the simulated barnacles on the glass sheet (about 1.75 MPa). Overall, examples 34, 35, 36, 37 still showed low simulated barnacle desorption. This shows that the amphoteric ion modified organosilicon coating can improve the antifouling capacity of the coating and maintain good fouling desorption capacity.

As shown in fig. 15, the greatest number of colonies was observed for example 34 compared to the other less colonies, indicating that the coating of example 34 had poorer antimicrobial properties, with increasing zwitterionic content. The coating has increasing antimicrobial properties.

It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The organic silicon-oxime urethane self-repairing antifouling coating based on nano silver is characterized in that the structural formula of the coating material is as follows:

wherein n, x and y are natural numbers larger than zero.

2. The preparation method of the nano-silver based silicone-oxime urethane self-repairing antifouling coating according to claim 1, comprising the following steps:

3. The preparation method of the nano-silver-based organosilicon-oxime urethane self-repairing antifouling coating is characterized in that n is 6-18;

or the addition amount of Polytetrahydrofuran (PTMG) is 5-20% of the mass of the double-end hydroxypropyl polydimethylsiloxane;

or the addition amount of the 2-hydroxyethyl disulfide is 20-60% of the molar weight of the double-end hydroxypropyl polydimethylsiloxane;

or the addition amount of the dimethylglyoxime is 50-150% of the molar weight of the hydroxypropyl polydimethylsiloxane at the double ends;

or the prepolymer reaction temperature is 50-70 ℃, the most preferable temperature is 65 ℃, and the reaction time is 1-4 h;

or, metal Cu ²⁺ The molar ratio of the DMG to the ligand is kept at 1: 2-4;

or the addition amount of AgNPs is 3% -9% of double-end hydroxypropyl polydimethylsiloxane;

or after AgNPs are added, stirring vigorously for 2-5 h;

or, the solvent is tetrahydrofuran;

or the relative molecular weight of the double-end hydroxypropyl polydimethylsiloxane is 1000-3000;

or the molar ratio of the double-end hydroxypropyl polydimethylsiloxane to the isophorone diisocyanate is 1: 1.5 to 4, and preferably 1: 2.4;

or the addition amount of the dibutyltin dilaurate is 0.5 wt% of the total mass of the double-end hydroxypropyl polydimethylsiloxane.

4. A silicone antifouling coating with fluorescent response is characterized in that the structural formula of the coating material is as follows:

wherein n and x are natural numbers larger than zero.

5. A method for preparing a silicone antifouling coating with a fluorescent response according to claim 4, comprising:

uniformly mixing the isocyanate-terminated prepolymer with 3, 4-diamino furoxan DAF and 7-amino-4-methylcoumarin AMC, continuing to react, and adding ZnCl after the reaction is finished ₂ And (4) continuing the reaction, and removing the solvent after the reaction is finished to obtain the catalyst.

6. The method of preparing a silicone antifouling coating having a fluorescent response according to claim 5, wherein n-6-20;

or, the isocyanate is isophorone diisocyanate;

or the addition amount of the 1, 4-butanediol is 80-120% of the molar weight of the double-end hydroxypropyl polydimethylsiloxane;

or the addition amount of the 7-amino-4-methylcoumarin AMC is 0.02g to 0.04 g;

or the reaction temperature is 60-90 ℃, and the reaction time is 1-4 h;

or, metallic Zn ²⁺ The molar ratio of the ligand to the DAF is 1: 2-4;

or, the solvent is tetrahydrofuran;

or the reaction temperature is 60-90 ℃, and the most preferable temperature is 70 ℃;

or the molar ratio of the double-end hydroxypropyl polydimethylsiloxane to the isophorone diisocyanate is 1: 1-5;

or the addition amount of dibutyltin dilaurate is 0.5 wt% of the total mass of the isocyanate-terminated prepolymer.

7. An organic silicon polyurethane marine antifouling coating containing zwitter-ion side chains is characterized in that the structural formula of the coating material is as follows:

wherein n, x and p are natural numbers larger than zero.

8. A method of preparing the marine antifouling coating of silicone polyurethane containing zwitterionic side chains according to claim 7, comprising:

mixing the prepolymer with PDEM (OH) ₂ Reacting, adding 1,4-BD and a catalyst after the reaction is finished, continuing the reaction, and adding TEOA for reacting for 1 hour after the reaction is finished to obtain a polymer;

9. The method of preparing the marine antifouling coating of organosilicon polyurethane containing zwitterionic side chains of claim 8, wherein the structural formula of the dihydroxy-terminated zwitterionic precursor is as follows:

wherein p is 7-15.

10. The method for preparing the marine antifouling organosilicon polyurethane coating containing zwitterionic side chains as claimed in claim 8, wherein p is 7-15, x is 8-12, n is 7-20;

or the molar ratio of DEM to TPG is 5:1,10: 1,20: 1;

or the initiator is azobisisobutyronitrile AIBN;

or the dosage of the initiator is 0.1 to 0.3 percent of the total mass of the DEM;

or, the solvent is THF;

or, the reaction temperature is 60-80 ℃, and the most preferable is 70 ℃;

or the addition amount of the zwitterion accounts for 0%, 5%, 10% and 14% of the total mass;

or, the relative molecular weight of the hydroxypropyl polydimethylsiloxane is 2000.