阅读说明：本技术 一种两亲性苯并噁嗪和聚乙二醇改性有机硅树脂及制备方法与应用 (Amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin and preparation method and application thereof ) 是由 辛忠 周长路 于 2019-04-29 设计创作，主要内容包括：本发明公开了一种两亲性苯并噁嗪和聚乙二醇改性有机硅树脂,是由苯并噁嗪官能化硅氧烷、聚乙二醇官能化硅氧烷与聚二甲基硅氧烷水解缩合反应制备得到。所述两亲性苯并噁嗪和聚乙二醇改性有机硅树脂是由以下重量份的组分制成：苯并噁嗪官能化硅氧烷30～50份、聚乙二醇官能化硅氧烷20～40份、聚二甲基硅氧烷10～50份。本发明提供的两亲性苯并噁嗪和聚乙二醇改性有机硅树脂是一种原位具有无氟两亲性共聚物,防污性能优异,制备方法简单,材料成本低,有望成为一种环境友好型防污新材料。(The invention discloses amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin which is prepared by the hydrolytic condensation reaction of benzoxazine functionalized siloxane, polyethylene glycol functionalized siloxane and polydimethylsiloxane. The amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin is prepared from the following components in parts by weight: 30-50 parts of benzoxazine-functionalized siloxane, 20-40 parts of polyethylene glycol-functionalized siloxane and 10-50 parts of polydimethylsiloxane. The amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin provided by the invention is an in-situ fluorine-free amphiphilic copolymer, has excellent antifouling performance, is simple in preparation method and low in material cost, and is expected to become an environment-friendly antifouling new material.)

1. An amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin is characterized in that: is prepared by the hydrolytic condensation reaction of benzoxazine functionalized siloxane, polyethylene glycol functionalized siloxane and polydimethylsiloxane.

2. The amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 1, wherein: the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin is prepared from the following components in parts by weight: 30-50 parts of benzoxazine-functionalized siloxane, 20-40 parts of polyethylene glycol-functionalized siloxane and 10-50 parts of polydimethylsiloxane.

3. The amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 2, wherein: the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin is prepared from the following components in parts by weight: 30-40 parts of benzoxazine-functionalized siloxane, 25-30 parts of polyethylene glycol-functionalized siloxane and 30-45 parts of polydimethylsiloxane.

4. The amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 1, wherein: the structure of the benzoxazine-functional siloxane is as follows:

wherein R is₁Is selected from C₁～C₁₈Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups₁～C₁₀One of a linear, branched or cyclic alkyl group;

R₃selected from methoxy or ethoxy.

5. The amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 1, wherein: the structure of the polyethylene glycol functionalized siloxane is as follows:

wherein R is₂One selected from methoxyl, amino, aldehyde group, carboxyl, sulfydryl, alkynyl and azido;

R₄selected from methoxy or ethoxy; n is 20 to 500.

6. The amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 1, wherein: the polydimethylsiloxane is dihydroxy polydimethylsiloxane, and the viscosity of the polydimethylsiloxane is 20-10000mPa & s.

7. A method of preparing the amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:

according to the proportion, the benzoxazine functionalized siloxane, the polyethylene glycol functionalized siloxane and the polydimethylsiloxane are dissolved in an organic solvent, water is added, then the pH value is adjusted, and the mixture is coated on a substrate for hydrolytic condensation to obtain the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin.

8. The method for preparing amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 7, wherein: the organic solvent is at least one of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, pyrrolidones and sulfoxides;

the pH value is adjusted by acid or alkali;

adjusting the pH value to 4-10;

the base material is at least one of metal and glass;

the temperature of the hydrolytic condensation is 25-150 ℃, and the reaction time is 1-24 h.

9. Use of an amphiphilic benzoxazine according to any one of claims 1 to 6 and a polyethylene glycol modified silicone resin as an antifouling coating.

10. Use of amphiphilic benzoxazine and polyethylene glycol modified silicone resin according to claim 9 as antifouling coating, characterized in that: the method comprises the following steps: and thermally curing the amphiphilic benzoxazine and the polyethylene glycol modified organic silicon resin to obtain the amphiphilic polybenzoxazine and polyethylene glycol modified organic silicon resin coating.

Technical Field

The invention belongs to the technical field of biomedical and marine antifouling materials, and particularly relates to amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin, a preparation method and application thereof.

Background

In the biomedical field, when protein is contacted with an in-vivo implanted apparatus, nonspecific adsorption is very easy to occur on the surface of a material to pollute the apparatus, the service efficiency and the service life of the apparatus are reduced, and serious hazards such as blood coagulation factor adsorption and platelet adhesion to form thrombus, bacterial infection and the like are caused. On the other hand, in the field of marine industry, marine organisms such as barnacles, mussels, diatoms and secretions thereof gradually attach to the surface of a marine engineering facility along with the service life of the marine engineering facility, so that the problems of reducing ship speed, increasing oil consumption, shielding sonar, corroding equipment and the like are caused, and the performance and safe and effective operation of the marine facility are seriously influenced. Therefore, the reduction of protein adsorption and marine organism attachment has great economic value and social benefits for the development of biomedicine and marine economy.

The antifouling coating material has two main design schemes according to the action mechanism: 1) anti-soiling (AF) coatings, a strategy aimed at preventing the adhesion of dirt during initial contact with the coating; 2) fouling-release (FR) coatings do not themselves prevent the attachment of dirt, but can attenuate the forces between the dirt and the coating surface to cause the dirt to peel off as the marine facility moves or as the mild "carding" equipment generates water flow shear forces. Both solutions are non-exclusive, and the final purpose is to achieve the purpose of unfavorable dirt adhesion or long-term adhesion by regulating the physicochemical properties or material properties (such as friction coefficient and elastic modulus) of the coating. The AF coating is represented by a hydrophilic material, and the surface can be highly hydrated through strong interaction (such as hydrogen bond formation with water molecules) with a water environment to generate hydration repulsion, so that the attraction of the surface of the material to adhesion objects such as protein and the like is greatly weakened, and the adhesion is further prevented. The FR coating is represented by a hydrophobic material, and mainly utilizes the property of low surface free energy of the FR coating to reduce the high-strength adhesion of various organisms to the surface of the FR coating; even if the organism is adhered by weak interface adhesion, the organism can be washed and desorbed under the action of external force to achieve the effect of resisting biological adhesion. However, because proteins are amphiphilic macromolecules and have a variety of varieties, marine environments are complex and changeable, and marine organisms are diverse, a single coating antifouling scheme is difficult to meet the broad-spectrum antifouling purpose, and therefore, a novel multifunctional material combining strong desorption of a hydrophobic material, adhesion resistance of a hydrophilic material and other antifouling capabilities gradually becomes a breakthrough for realizing a broad-spectrum antifouling technology of the coating.

The organosilicon polymer is an excellent antifouling coating main body material due to the characteristics of low surface energy and low elastic modulus because of having a linear flowable main chain and enough surface hydrophobic side groups, but the organosilicon polymer has the defects of low mechanical strength and poor adhesion of a substrate, and other materials are often required to be introduced for improvement. Chinese patents CN101531865A, CN105199070A, and CN106497302A respectively report that amphiphilic antifouling coatings using polyacrylamide microcapsules, inorganic nanomaterials, and polyurethane modified silicone resin all achieve better effects, but some of these materials are easy to release during use, and some of these materials sacrifice the advantage of low surface energy of silicone resin. Therefore, the fluorine-containing material with extremely low surface free energy is used as the modified material of the organic silicon resin and has more application value. Chinese patents CN101412779A, CN103450419A, CN103589298A report the work of fluorine-containing amphiphilic copolymer resin as a base material of antifouling coating, but fluorine-containing materials are expensive and have potential biohazard and have limitations in some applications.

Disclosure of Invention

In order to overcome the defects of high cost and biohazard of a fluorine-containing material modification method, the invention provides a low-cost, green and fluorine-free amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin.

The second purpose of the invention is to provide a preparation method of the amphiphilic benzoxazine and polyethylene glycol modified silicone resin.

The third purpose of the invention is to provide the application of the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin as the antifouling paint.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin, which is prepared by hydrolysis condensation reaction of benzoxazine functionalized siloxane, polyethylene glycol functionalized siloxane and polydimethylsiloxane.

The amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin is prepared from the following components in parts by weight: 30-50 parts of benzoxazine-functionalized siloxane, 20-40 parts of polyethylene glycol-functionalized siloxane and 10-50 parts of polydimethylsiloxane.

Preferably, the amphiphilic benzoxazine and polyethylene glycol modified silicone resin is prepared from the following components in parts by weight: 30-40 parts of benzoxazine-functionalized siloxane, 25-30 parts of polyethylene glycol-functionalized siloxane and 30-45 parts of polydimethylsiloxane.

The structure of the benzoxazine-functional siloxane is as follows:

Wherein R is₁Is selected from C₁～C₁₈Straight, branched or cyclic alkyl, halogen, phenyl, hydrogen or C substituted by amino, halogen, mercapto or epoxy groups₁～C₁₀One of a linear, branched or cyclic alkyl group;

R₃selected from methoxy or ethoxy.

The R is₁Preferably methyl, dodecyl (-C)₁₂H₂₅) N-butyl (-C)₄H₉)。

The structure of the polyethylene glycol functionalized siloxane is as follows:

wherein R is₂One selected from methoxyl, amino, aldehyde group, carboxyl, sulfydryl, alkynyl and azido;

R₄selected from methoxy or ethoxy; n is 20 to 500.

The Polydimethylsiloxane (PDMS) is dihydroxy polydimethylsiloxane, and has a viscosity of 20-10000 mPas, preferably 50-1000 mPas.

The second aspect of the invention provides a preparation method of the amphiphilic benzoxazine and polyethylene glycol modified silicone resin, which comprises the following steps:

according to the proportion, the benzoxazine functionalized siloxane, the polyethylene glycol functionalized siloxane and the polydimethylsiloxane are dissolved in an organic solvent, water is added, then the pH value is adjusted, and the mixture is coated on a substrate for hydrolytic condensation to obtain the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin.

The organic solvent is selected from at least one of alkanes, substituted alkanes, alcohols, ethers, ketones, esters, amides, pyrrolidones and sulfoxides, preferably at least one of trichloromethane, tetrachloroethane, ethanol, N-butanol, diethylene glycol dimethyl ether, tetrahydrofuran, acetone, ethyl acetate, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.

The dosage of the organic solvent is 1-1000% of the mass sum of the benzoxazine functionalized siloxane and the polyethylene glycol functionalized siloxane.

The mole number of the water is 0.01 to 50 times of the sum of the moles of the benzoxazine-functionalized siloxane and the polyethylene glycol-functionalized siloxane.

The pH value is adjusted by selecting acid and alkali, the acid is hydrochloric acid or acetic acid, and the alkali is at least one of sodium hydroxide, ammonia water and triethylamine.

And adjusting the pH value to 4-10.

The base material is at least one of metal and glass, and is specifically selected from aluminum sheets, magnesium alloy sheets, glass sheets, stainless steel materials and titanium alloy sheets.

The temperature of the hydrolytic condensation is 25-150 ℃, and preferably 30-130 ℃; the reaction time is 1-24h, preferably 2-15 h.

The third aspect of the invention provides a use of the amphiphilic benzoxazine and polyethylene glycol modified silicone resin as an antifouling paint.

The application of the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin as an antifouling paint comprises the following steps: and thermally curing the amphiphilic benzoxazine and the polyethylene glycol modified organic silicon resin to obtain the amphiphilic polybenzoxazine and polyethylene glycol modified organic silicon resin coating which is used as an antifouling coating and mainly used for biological medicines or marine antifouling coatings.

The curing temperature of the thermal curing is 120-260 ℃, and preferably 150-220 ℃; the curing time is 0.1 to 24 hours, preferably 0.5 to 3 hours.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the amphiphilic benzoxazine and polyethylene glycol modified organic silicon resin provided by the invention is an in-situ fluorine-free amphiphilic copolymer, has excellent antifouling performance, is simple in preparation method and low in material cost, and is expected to become an environment-friendly antifouling new material.

The amphiphilic polybenzoxazine and polyethylene glycol modified organic silicon resin coating provided by the invention can reduce the coating cost, meet the environment-friendly requirement of the coating and improve the antifouling performance of the coating. The invention utilizes the low surface energy characteristic that polybenzoxazine has a similar fluorine-containing compound and does not depend on fluorine element to replace a fluorine-containing structure used in the existing low surface energy antifouling material, thereby avoiding the problems of high application cost and potential hazard to organisms of the fluorine-containing material.

According to the amphiphilic polybenzoxazine and polyethylene glycol modified organic silicon resin coating provided by the invention, through the structural design of siloxane in the components, the components have good compatibility, and can be fully reacted and crosslinked in a hydrolytic condensation process to prepare a coating with a smooth surface.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.