Amphiphilic organic silicon coating and preparation method and application thereof

文档序号：1947924 发布日期：2021-12-10 浏览：4次中文

阅读说明：本技术 一种两亲性有机硅涂层及其制备方法与应用 (Amphiphilic organic silicon coating and preparation method and application thereof ) 是由刘月涛宋程新王哲张德金高传慧王传兴武玉民于 2021-09-16 设计创作，主要内容包括：本发明涉及一种两亲性有机硅涂层及其制备方法与应用,将硫代甘油、丙烯酸丁酯、N-乙烯吡咯烷酮反应,得到一种亲水端基化合物；亲水端基化合物作为侧链引入主链中,形成一种梳状结构,通过缩合反应合成一种两亲性有机硅涂层。该有机硅涂层并具有优异的机械强度,较低的表面能。亲水端基的存在改变了有机硅的疏水性,可以形成一种“模糊”表面,不利于海洋生物附着。本发明的两亲性有机硅涂层制备方法新颖、操作方便、实用性强,在海洋防污领域具有广阔的应用前景。(The invention relates to an amphiphilic organic silicon coating and a preparation method and application thereof, wherein thioglycerol, butyl acrylate and N-vinyl pyrrolidone are reacted to obtain a hydrophilic end group compound; hydrophilic end group compound is introduced into the main chain as a side chain to form a comb-shaped structure, and an amphiphilic organic silicon coating is synthesized through condensation reaction. The organic silicon coating has excellent mechanical strength and lower surface energy. The presence of hydrophilic end groups changes the hydrophobicity of the silicone, which can form a 'fuzzy' surface, which is not beneficial to marine organism attachment. The preparation method of the amphiphilic organic silicon coating is novel, convenient to operate and high in practicability, and has a wide application prospect in the field of marine antifouling.)

1. A hydrophilic end-group compound having the structure of formula (i):

in the formula (I), x is 1-5, and y is 1-5.

2. The method for preparing a hydrophilic end group compound according to claim 1, comprising the steps of:

mixing thioglycerol, Butyl Acrylate (BA), N-vinyl pyrrolidone (NVP) and a solvent, adding an initiator, reacting for 10-15 hours at 60-90 ℃ under the condition of introducing nitrogen, decompressing to remove the solvent after the reaction is finished, precipitating a product in excessive petroleum ether, and then drying in vacuum to obtain the catalyst.

3. The method for preparing a hydrophilic end group compound according to claim 2, wherein the molar ratio of thioglycerol, Butyl Acrylate (BA) and N-vinylpyrrolidone (NVP) is 1: (2-5): (2-5);

preferably, the initiator is Azobisisobutyronitrile (AIBN);

preferably, the addition amount of the initiator is 0.5-1.0% of the total molar amount of Butyl Acrylate (BA) and N-vinyl pyrrolidone (NVP);

preferably, the solvent is tetrahydrofuran.

4. The method for preparing a hydrophilic end group compound according to claim 2, wherein the reaction temperature is 70 to 80 ℃;

preferably, the vacuum drying temperature is 70-90 ℃.

5. Use of the hydrophilic end group compound according to claim 1 as a hydrophilic modification group for an amphiphilic silicone coating.

6. An amphiphilic silicone polymer having the structure of formula (ii):

in the formula (II), a, b, x, y and n are all natural numbers which are larger than zero.

7. The method of preparing the amphiphilic silicone polymer of claim 6, comprising the steps of:

the amphiphilic organic silicon polymer is prepared by taking isocyanate-terminated prepolymer as a main material, 1, 4-butanediol as a chain extender, a hydrophilic end group compound as a side chain and triethanolamine as a cross-linking agent through a polycondensation reaction.

8. The method for preparing the amphiphilic organosilicon polymer according to claim 7, wherein the amount of the hydrophilic end group compound is 5-15% of the mass ratio of the isocyanate-terminated prepolymer;

preferably, the addition amount of the 1, 4-butanediol is 150% of the molar weight of the isocyanate-terminated prepolymer;

preferably, the addition amount of the triethanolamine is 20 to 40 percent of the molar weight of the isocyanate-terminated prepolymer;

preferably, the reaction temperature is 60 to 90 ℃.

9. Use of the amphiphilic silicone polymer of claim 6 as a coating material.

10. A marine service coating characterized in that said coating is an amphiphilic silicone polymer according to claim 6.

Technical Field

The invention belongs to the field of intelligent organic silicon high polymer materials, and particularly relates to an amphiphilic organic silicon coating and a preparation method and application thereof.

Background

In order to make full use of various resources in the ocean, a large number of marine facilities are used for the development and utilization of marine resources, but in a complex marine environment, marine biofouling becomes an urgent problem to be solved. Efforts have been made to develop coatings that effectively block the attachment of marine organisms. TBT coatings have excellent antifouling properties, but pose a serious threat to the environment and have been banned globally in 2008. Therefore, the development of environment-friendly antifouling coatings is a current research hotspot.

The organic silicon coating has the advantages of low surface energy, excellent high and low temperature resistance, excellent radiation resistance, excellent oxidation resistance and the like due to the specific Si-O-Si structure of the main chain and the methyl on the side chain, and is nontoxic and environment-friendly, thereby being widely favored by people. The coating can enable the fouling to be easily removed by washing water in the sailing process of a ship, but under the static condition, the shear force provided by water flow is lacked, and the problem of insufficient antifouling capacity exists in the organic silicon coating. Some researchers add antifouling agents to the silicone coating to achieve antifouling effect, such as small molecule silicone oil, capsaicin, etc., although the antifouling effect is good, the release rate is unstable, and once the antifouling agents are completely released, the antifouling capability of the coating is reduced or even lost, so that the service life of the coating is shortened, and therefore, the development of an environment-friendly coating material which can maintain the antifouling capability for a long time is required.

The amphiphilic polymer coating consists of a low-surface-energy hydrophobic component and a hydrophilic component, the hydrophobicity of the material is changed by the hydrophilic component, a 'fuzzy' surface can be formed, the adhesion of marine bacteria and diatoms is not facilitated, and the amphiphilic polymer coating has a wide application prospect in the field of marine antifouling in the future. The low surface energy hydrophobic component is generally referred to as a silicone material, but the existing silicone low surface energy materials are soft and have poor mechanical properties, so that the materials are not durable and are easily damaged by machinery, which greatly limits the application range of the materials. In order to improve the problem of poor mechanical properties of silicone materials, some researchers introduce polyurea or urethane structures and the like, and provide a large amount of hydrogen bonds, so that the mechanical strength of the materials can be greatly enhanced, but the improvement is still insufficient.

There are also patent documents on amphiphilic silicones, for example: CN112812307A discloses a single-end-capped amphiphilic organosiloxane macromonomer, a silicone hydrogel, a corneal contact lens and a preparation method thereof, wherein a silicone hydrogel material is synthesized by physically blending the amphiphilic organosiloxane macromonomer with a hydrophilic small molecular monomer; CN107488407A discloses an organosilicon modified alkyd resin water-based emulsion and a preparation method thereof, which relate to an amphiphilic organosilicon modifier with strong hydrophilicity but still insufficient mechanical properties.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides an amphiphilic organic silicon coating and a preparation method and application thereof. The invention changes the hydrophobicity of the material by introducing the hydrophilic end group polymer, the carbamate provides a large amount of hydrogen bonds, and the triethanolamine constructs a stable covalent cross-linking network, thereby greatly improving the mechanical property of the material. The invention enables the material to have higher mechanical strength based on hydrogen bond interaction and a three-dimensional cross-linking structure, and the hydrophilic end group compound does not influence the characteristic of low surface free energy while changing the hydrophobicity of the material. The amphiphilic organic silicon coating is prepared by reacting dihydric alcohol with isocyanate to synthesize an isocyanate-terminated prepolymer, and then taking 1, 4-butanediol as a chain extender, a hydrophilic end group compound as a side chain and triethanolamine as a cross-linking agent.

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

according to the invention, firstly, a hydrophilic end group compound is provided, and the hydrophilic end group compound is used as a side chain to form a macromolecular linear polymer with a prepolymer, and the macromolecular linear polymer is reacted to obtain the amphiphilic organic silicon coating.

A hydrophilic end group compound having the structure of formula (I):

in the formula (I), x is 1-5, and y is 1-5; further preferably, x is 3 and y is 3.

According to the present invention, the above method for preparing a hydrophilic end group compound comprises the steps of:

According to the invention, the preferred molar ratio of thioglycerol, Butyl Acrylate (BA), N-vinylpyrrolidone (NVP) is 1: (2-5): (2-5), further preferably 1: 2.5: 2.5.

according to the present invention, preferably, the initiator is Azobisisobutyronitrile (AIBN);

preferably, the initiator is added in an amount of 0.5 to 1.0% based on the total molar amount of Butyl Acrylate (BA) and N-vinylpyrrolidone (NVP).

According to the present invention, preferably, the solvent is tetrahydrofuran.

According to the invention, the reaction temperature is preferably from 70 to 80 ℃ and most preferably 75 ℃.

According to the invention, the vacuum drying temperature is preferably 70 to 90 ℃, most preferably 80 ℃.

According to the present invention, the method for preparing the hydrophilic end group compound, a preferred embodiment, comprises the steps of:

mixing thioglycerol, Butyl Acrylate (BA), N-vinyl pyrrolidone (NVP) according to the weight ratio of 0.4: 1: 1, adding the mixture into a three-neck flask provided with a mechanical stirring paddle and a condensing system, wherein Azodiisobutyronitrile (AIBN) is used as an initiator, and the using amount of the Azodiisobutyronitrile (AIBN) is 1 percent of the total molar amount of BA and NVP; using tetrahydrofuran as solvent and N₂Degassing, heating to 75 ℃ and reacting for 12 hours; removing most of the solvent under reduced pressure, and precipitating in excess petroleum ether; finally, the product was transferred to a round bottom flask and dried overnight in a vacuum oven at 80 ℃.

According to the invention, the hydrophilic end group compound is used as a hydrophilic modification group of an amphiphilic organic silicon coating.

The invention changes the hydrophobicity of the organic silicon coating by introducing the hydrophilic end group compound into the side chain, and has no great influence on the characteristic of low surface energy. Butyl Acrylate (BA) and N-vinyl pyrrolidone (NVP) with strong hydrophilicity and stable chemical properties are selected as hydrophilic groups, and thioglycerol enables hydrophilic end group compounds to be introduced as side chains. Compared with the method using polyethylene glycol as a hydrophilic group, the polyethylene glycol is not stable enough in seawater, ether bonds can be broken, the hydrophilicity of the material is increased along with the increase of the content of the hydrophilic end group compound, the surface energy is gradually increased, but the maximum value is only 24.43 mJ.m^-2The research shows that the surface energy is not more than 30 mJ.m^-2I.e., has no effect on the soil release capacity, and is still a low surface energy material.

According to the present invention, there is also provided an amphiphilic silicone polymer having a structure represented by formula (ii):

in the formula (II), a, b, x, y and n are all natural numbers which are larger than zero.

According to the invention, it is preferred that in formula (ii), a is 1 to 5, b is 1 to 5, x is 8 to 12, y is 9 to 20, and n is 7 to 20.

According to the invention, the preparation method of the amphiphilic organic silicon polymer comprises the following steps:

According to the invention, the addition amount of the hydrophilic end group compound is preferably 5-15% of the mass ratio of the isocyanate-terminated prepolymer;

preferably, the addition amount of the 1, 4-butanediol is 150% of the molar weight of the isocyanate-terminated prepolymer;

preferably, triethanolamine is added in an amount of 20 to 40% by mole based on the isocyanate-terminated prepolymer.

According to the invention, the reaction temperature is preferably 60 to 90 ℃ and the reaction time is preferably 1 to 3 hours.

According to the present invention, the isocyanate terminated prepolymer is preferably prepared by the following method:

mixing hydroxypropyl polydimethylsiloxane, polytetrahydrofuran 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.

According to the present invention, preferably, the relative molecular weight of the hydroxypropyl polydimethylsiloxane is 1000-3000;

preferably, the polytetrahydrofuran has a relative molecular weight of 1000-2000.

According to the present invention, it is preferred that the molar ratio of hydroxypropyl polydimethylsiloxane, polytetrahydrofuran and isophorone diisocyanate is 1: (0.25-1): (3-7), further preferably 1: 0.5: 5.

according to the present invention, it is preferable that dibutyltin dilaurate be added in an amount of 0.5% by mass based on the total mass of the isocyanate terminated prepolymer.

According to the present invention, a method for preparing an amphiphilic silicone polymer, a preferred embodiment, comprises the steps of:

adding 8g of hydroxypropyl polydimethylsiloxane (Mn: 2000), 2g of polytetrahydrofuran (Mn: 1000) and 4.8g of isophorone diisocyanate into a three-neck flask provided with a mechanical stirring paddle, a nitrogen circulating system and a condensing system, adding 0.1g of dibutyltin dilaurate as a catalyst and tetrahydrofuran as a solvent, completely dissolving, and reacting at 70 ℃ for 1h under the protection of nitrogen to obtain an isocyanate-terminated prepolymer;

then adding 0.9g of 1, 4-butanediol and a hydrophilic end group compound as a chain extender and a side chain respectively, wherein the adding amount of the hydrophilic end group is 5 percent of the total mass of reactants, continuing to react for 2.5 hours, finally adding 0.4g of triethanolamine as a cross-linking agent, continuing to react for 1 hour to obtain colorless liquid, and evaporating the solvent to obtain the amphiphilic organic silicon polymer.

According to the invention, the amphiphilic silicone polymers described above are used as coating materials.

According to the invention, a marine facility coating is also provided, and the coating is the amphiphilic organic silicon polymer.

The principle of the invention is as follows:

according to the invention, hydroxypropyl polydimethylsiloxane main material is added with a small amount of polytetrahydrofuran, 1, 4-butanediol is used as a chain extender, a hydrophilic end group compound is used as a side chain, and triethanolamine is used for crosslinking to prepare an amphiphilic organic silicon polymer which can be used as a coating. The N-vinyl pyrrolidone of the hydrophilic end group compound has strong hydrophilicity, the hydrophilicity of the amphiphilic organic silicon polymer coating can be improved to a great extent, the stability of the hydrophilic end group is enhanced by butyl acrylate, the amphiphilic organic silicon coating is functionalized by mercaptoethanol, and the synthesized amphiphilic organic silicon coating has good mechanical property.

The invention has the following beneficial effects;

1. the hydrophilic end group compound is synthesized by free radical polymerization by using a hydrophilic monomer with strong hydrophilicity and stable chemical properties, and the preparation method is simple.

2. The amphiphilic organic silicon polymer is completely nontoxic and has good mechanical properties. The carbamate structure provides rich hydrogen bonds, the material has higher mechanical strength by virtue of the interaction of the hydrogen bonds and the three-dimensional cross-linking structure, and the rich hydrogen bonds can also greatly improve the problems of poor adhesive force and easy peeling of the low-surface-energy organosilicon material and the base material.

3. The reaction condition is simple, the controllability is good, the hydrophobicity of the material is changed by introducing the hydrophilic end group into the side chain of the amphiphilic organic silicon coating, the influence on the characteristic of low surface energy is not great, although the surface energy is gradually increased, the maximum value is only 24.43 mJ.m^-2(less than 30 mJ. m)^-2) It has no influence on the dirt release capacity and is still a low surface energy material. Has wide application prospect in the field of marine antifouling.

Drawings

FIG. 1 is an infrared spectrum of a hydrophilic end group compound prepared in example 1 of the present invention.

FIG. 2 is an IR spectrum of the amphiphilic silicone coating prepared in inventive example 1.

FIG. 3 is a drawing of amphiphilic silicone coatings prepared in inventive examples 1-3 and comparative example 1.

Fig. 4 is a graph of contact angle and surface free energy for amphiphilic silicone coatings prepared in examples 1-3 of the present invention and comparative example 1.

Detailed Description

The features of the present invention and other related features are described in further detail below by way of examples to facilitate understanding by persons skilled in the art, but are not limited thereto.

Example 1

Mixing thioglycerol, Butyl Acrylate (BA), N-vinyl pyrrolidone (NVP) according to the weight ratio of 0.4: 1: 1 was added to a 250ml three-necked flask equipped with a mechanical stirring blade and a condensation system. Azobisisobutyronitrile (AIBN) was used as an initiator in an amount of 1% of the total molar amount of BA and NVP. Tetrahydrofuran as solvent and N₂And (4) degassing. The temperature is raised to 75 ℃ for reaction for 12 hours. Most of the solvent was removed under reduced pressure and precipitated in excess petroleum ether. The precipitate was collected and dried in a vacuum oven at 80 ℃ overnight to give the hydrophilic end group compound.

8g of hydroxypropyl polydimethylsiloxane (Mn: 2000) and 2g of polytetrahydrofuran (Mn: 1000) and 4.8g 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 1 hour, so that the prepolymer terminated by isocyanate is obtained. Then adding 0.9g of 1, 4-butanediol and the hydrophilic end group compound synthesized in the previous step as a chain extender and a side chain respectively, wherein the adding amount of the hydrophilic end group compound is 5 percent of the total mass of the isocyanate-terminated prepolymer, continuing to react for 2.5 hours, finally adding 0.4g of triethanolamine as a cross-linking agent, continuing to react for 2 hours to obtain colorless liquid, and evaporating the solvent to obtain the amphiphilic organic silicon coating product.

Example 2