阅读说明：本技术 一种含氟自抛光树脂基超滑涂层材料的制备方法 (Preparation method of fluorine-containing self-polishing resin-based super-smooth coating material ) 是由 王君 李亚坤 陈蓉蓉 张宏森 刘琦 于静 刘婧媛 宋大雷 于 2019-09-05 设计创作，主要内容包括：本发明提供的是一种含氟自抛光树脂基超滑涂层材料的制备方法。一：将含氟丙烯酸酯单体、含羧基丙烯酸单体、甲基丙烯酸甲酯以及丙烯酸乙酯在总量的重量比5～45:10～55:5～15：10～30比例下80℃下反应6小时,合成得到树脂基体；二：将所得到的树脂基体与吡啶三苯基硼烷在总量的重量比70～90:5～30的比例下在90℃下反应4小时。由于树脂基体的自抛光作用,润滑油渗出到涂层表面的距离不会增加,可保证润滑油恒定的渗出速率；当涂层中的润滑油消耗殆尽后,涂层树脂基体依然可以通过自抛光作用防止污损生物在底材上附着。本发明制备的涂层解决了润滑油容易流失而导致涂层失效的问题,是一种环保长效的防污涂层。(The invention provides a preparation method of a fluorine-containing self-polishing resin-based super-smooth coating material. Firstly, the method comprises the following steps: mixing a fluorine-containing acrylate monomer, a carboxyl-containing acrylic monomer, methyl methacrylate and ethyl acrylate in a weight ratio of 5-45: 10-55: 5-15: reacting for 6 hours at 80 ℃ in a proportion of 10-30 to obtain a resin matrix; II, secondly: and reacting the obtained resin matrix with pyridine triphenylborane at the total weight ratio of 70-90: 5-30 at 90 ℃ for 4 hours. Due to the self-polishing effect of the resin matrix, the distance of the lubricating oil seeping out of the surface of the coating cannot be increased, and the constant seepage rate of the lubricating oil can be ensured; when the lubricating oil in the coating is used up, the resin matrix of the coating still can prevent fouling organisms from attaching on the substrate through self-polishing effect. The coating prepared by the invention solves the problem that the coating is ineffective due to the easy loss of lubricating oil, and is an environment-friendly long-acting antifouling coating.)

1. A preparation method of a fluorine-containing self-polishing resin-based super-smooth coating material is characterized by comprising the following steps:

the method comprises the following steps: mixing a fluorine-containing acrylate monomer, a carboxyl-containing acrylic monomer, methyl methacrylate and ethyl acrylate in a weight ratio of 5-45: 10-55: 5-15: reacting for 6 hours at 80 ℃ in a proportion of 10-30 to obtain a resin matrix;

step two: and reacting the obtained resin matrix with pyridine triphenylborane at the total weight ratio of 70-90: 5-30 at 90 ℃ for 4 hours to obtain the coating material.

2. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 1, which is characterized in that: weighing perfluoropolyether lubricating oil accounting for 0.5-10% of the total weight of the mixture according to the proportion, adding the perfluoropolyether lubricating oil into the obtained coating material, and simultaneously carrying out ultrasonic dispersion treatment to pre-disperse the perfluoropolyether lubricating oil in the coating material; dip-coating a coating material coating on the pretreated substrate, and air-drying the coating material coating at the temperature of 15-45 ℃ to obtain the fluorine-containing self-polishing resin-based super-smooth coating.

3. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 2, which is characterized in that: the time of the ultrasonic dispersion treatment is 180 s.

4. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 3, which is characterized in that: the fluorine-containing acrylate monomer is hexafluorobutyl methacrylate.

5. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 4, which is characterized in that: the acrylic monomer containing carboxyl is acrylic acid.

6. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 5, which is characterized in that: the acid value range of the resin matrix obtained by synthesis is 80-120 mgKOH/g.

7. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 6, which is characterized in that: the addition amount of the perfluoropolyether lubricating oil is 1-9 wt%.

8. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 7, which is characterized in that: the fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane.

9. The method for preparing the fluorine-containing self-polishing resin-based ultra-smooth coating material according to claim 8, which is characterized in that: the temperature range of the coating airing is 20-40 ℃.

Technical Field

The invention relates to a preparation method of an antifouling coating, in particular to a preparation method of a self-polishing resin-based super-smooth coating.

Background

The existence of the marine fouling problem brings great inconvenience to people in the development of marine resources and marine military activities. Due to the unique oil layer protection effect of the ultra-smooth coating, the attachment of fouling organisms on the surface of the coating can be effectively prevented, and the harm caused by the fouling organisms is reduced.

However, the lubricating oil is easy to lose, so that the failure of the coating is a common problem of the super-smooth coating. The lubricating liquid can be quickly lost due to water flow scouring, external force damage, high temperature and ultraviolet irradiation, and once the lubricating liquid is lost, the hole structure on the surface of the ultra-smooth coating can provide attachment points for fouling organisms, so that the attachment of the fouling organisms is accelerated.

In order to solve the problems, a method for preparing a liquid autocrine super-slip coating with long-acting protection is provided in patent document with application number 201811241747.0 and name 'a liquid autocrine super-slip coating with long-acting protection and a preparation method'. According to the method, a porous structure is prepared in the coating through a pore-forming agent, and lubricating oil is poured into the porous structure to form the super-smooth coating. When the lubricating oil liquid layer on the surface of the coating is lost under the factors of external force and the like, the lubricating oil stored in the internal pore structure quickly seeps out of the lubricating oil to the surface of the coating, so that a supplementing effect is achieved. Although the method plays a role in slowly releasing the lubricating oil and prolonging the service life of the ultra-smooth coating, the following problems still exist:

1. empty holes are left after the lubricating oil in the hole structure close to the surface of the coating is used up, so that the lubricating oil in the hole structure at the bottom of the coating is prevented from being diffused to the surface of the coating, and the lubricating oil cannot be supplemented or the supplementing rate is reduced, so that the antifouling performance of the coating is failed;

2. after the lubricating oil in the coating hole structure is completely consumed, the remaining rough substrate of the coating provides an attachment site for marine fouling organisms, and the attachment of the fouling organisms is promoted;

3. the preparation process of the coating relates to the steps of high-temperature curing, pore-forming by a pore-forming agent and the like, and is complex and time-consuming. The above three disadvantages limit to some extent its application in the field of antifouling.

Therefore, the development of the ultra-smooth coating which is simple in preparation method and still has certain antifouling property after the lubricating oil is used up is of great significance.

Disclosure of Invention

The invention aims to provide a preparation method of a fluorine-containing self-polishing resin-based super-smooth coating material which is simple in preparation method and can still have certain antifouling property after lubricating oil is used up.

The purpose of the invention is realized as follows:

the method comprises the following steps: mixing a fluorine-containing acrylate monomer, a carboxyl-containing acrylic monomer, methyl methacrylate and ethyl acrylate in a weight ratio of 5-45: 10-55: 5-15: reacting at 80 ℃ for 6 hours according to the proportion of 10-30, and synthesizing;

step two: and reacting the obtained resin matrix with pyridine triphenylborane at the total weight ratio of 70-90: 5-30 at 90 ℃ for 4 hours to obtain the coating material.

The present invention may further comprise:

1. weighing perfluoropolyether lubricating oil accounting for 0.5-10% of the total weight of the mixture according to the proportion, adding the perfluoropolyether lubricating oil into the obtained coating material, and simultaneously carrying out ultrasonic dispersion treatment to pre-disperse the perfluoropolyether lubricating oil in the coating material; dip-coating a coating material coating on the pretreated substrate, and air-drying the coating material coating at the temperature of 15-45 ℃ to obtain the fluorine-containing self-polishing resin-based super-smooth coating.

2. The time of the ultrasonic dispersion treatment is 180 s.

3. The fluorine-containing acrylate monomer is preferably hexafluorobutyl methacrylate.

4. The carboxyl group-containing acrylic monomer is preferably acrylic acid.

5. The acid value range of the resin matrix obtained by synthesis is 80-120 mgKOH/g.

6. The addition amount of the perfluoropolyether lubricating oil is preferably 1-9 wt%.

7. The fluorine-containing silane coupling agent is preferably heptadecafluorodecyltrimethoxysilane.

8. The temperature range of the coating airing is preferably 20-40 ℃.

The invention provides a fluorine-containing self-polishing resin-based super-smooth coating, aiming at solving the problem that the coating fails due to the fact that lubricating oil is easy to run off in the prior art. According to the invention, a series of acrylic acid fluorine boron self-polishing resins with different self-polishing rates are prepared as a coating substrate by adjusting the length of a fluorine-containing side chain in the acrylic acid fluorine boron self-polishing resin and the acid value of the resin. The self-repairing acrylic acid fluorine boron ultra-smooth coating can be prepared by ultrasonically mixing lubricating oil and acrylic acid fluorine boron self-polishing resin and adopting a dip-coating mode. Lubricating oil exists in the coating in the form of micro-nano droplets, and after the lubricating oil on the surface of the coating is exhausted due to factors such as external force and the like, the lubricating oil droplets can seep supplementary lubricating oil to the surface to form an oil layer.

Compared with the conventional technology, the coating has the following advantages:

1. the invention does not need pore-forming agent to form pores, does not need heating and solidifying, and has simple preparation method.

2. As the hydrolyzable side chain is introduced in the synthesis process of the resin matrix, the coating matrix can gradually generate self-polishing action, the distance of the lubricating oil seeping out of the coating surface cannot be increased, and the constant seepage rate of the lubricating oil can be ensured.

3. When the lubricating oil in the coating is used up, the coating resin matrix of the fluorine-boron acrylate self-polishing resin can still prevent fouling organisms from attaching to the substrate through self-polishing.

The technical scheme of the invention is mainly characterized in that:

(1) preparation of resin matrix: mixing a fluorine-containing acrylate monomer, a carboxyl-containing acrylic monomer, methyl methacrylate and ethyl acrylate in a weight ratio of 10-65: 5-35: 5-15: reacting at the temperature of 80 ℃ for 6 hours in the proportion of 10-30 to synthesize the resin product a.

Technical description of this section: the acid value of the acrylic self-polishing resin synthesized in the conventional technology is 90-400 mgKOH/g. When the weight proportion of the acrylic acid is 5-35 parts in the mixture monomer, calculating the formula according to the acid value And the actual measurement of the volume of the used potassium hydroxide solution can calculate that the acid value is within the range of 80-120 mgKOH/g, which is slightly lower than the acid value of the acrylic acid self-polishing resin synthesized in the conventional technology. The relatively low acid number reduces the self-polishing rate of the resin matrix, thereby extending the useful life of the coating;

the glass transition temperature of the acrylic self-polishing resin can be adjusted by the kind and weight ratio of the acrylic monomer for synthesizing the resin. The glass transition of the acrylic self-polishing resin matrix is generally between-30 ℃ and 10 ℃, and when the weight ratio of the fluorine-containing acrylate monomer to the carboxyl-containing acrylic monomer to the methyl methacrylate to the ethyl acrylate is 10-65: 5-35: 5-15: when the ratio is in the range of 10-30, the formula 1/T is expressed by FOX_g＝W₁/T_g1+W₂/T_g2+W₃/T_g3+……W_n/T_gnThe glass transition temperature can be calculated to be between-20 ℃ and 8 ℃. Thereby synthesizingThe acrylic self-polishing resin can keep better performance in a low-temperature environment below zero ℃.

(2) And (3) reacting the product a with pyridine triphenylborane at the total weight ratio of 70-90: 5-30 at 90 ℃ for 4 hours to obtain a resin product b.

Technical description of this section: the weight ratio of the product a to the pyridine triphenylborane is 70-90: 5-30, so that the pyridine triphenylborane can completely react with carboxyl of a molecular side chain of the product a, and a small amount of excessive pyridine triphenylborane exists in the product b. During the self-polishing process of the resin matrix, the pyridine triphenylborane in the resin matrix can be released as an antifouling agent, and the antifouling property of the coating is enhanced.

(3) And weighing perfluoropolyether lubricating oil accounting for 0.5-10% of the total weight of the mixture according to the proportion, adding the perfluoropolyether lubricating oil into the product b, and simultaneously performing ultrasonic dispersion treatment for 180s to pre-disperse the perfluoropolyether lubricating oil in resin.

Technical description of this section: the technical difficulty of the invention is that the lubricating oil exists in the resin matrix in the form of micro-nano droplets, so that the lubricating oil is not easy to run off and consume, and the lubricating oil can be uniformly leaked and supplemented to the surface of the coating. Different from other lubricating oil, the perfluoropolyether lubricating oil exists in a micro-nano small droplet form in a synthesized acrylic acid fluorine boron resin matrix due to the fact that the perfluoropolyether lubricating oil contains more C-F bonds and smaller molecular mass; when the ultrasonic treatment time is shorter than 180s, the size of the lubricating oil droplets is larger and is distributed unevenly, and when the ultrasonic treatment time is more than or equal to 180s, the lubricating oil droplets are distributed evenly in the resin matrix, the size of the droplets is reduced to be within the range of 200 nm-5 um, the loss rate of the lubricating oil is greatly reduced, and the service life of the coating is prolonged.

(4) Wiping the substrate with absolute ethyl alcohol, removing oil stains and other impurities on the surface, drying by air blowing at 80 ℃, soaking in an ethanol solution containing a fluorine-containing silane coupling agent with the volume ratio of 5% for 120min, taking out, and drying to constant weight. And dip-coating an ultra-smooth coating with the dry film thickness of about 180 mu m on the treated substrate by adopting a dip-coating method, horizontally placing the coating, and airing the coating at the temperature of 15-45 ℃.

Technical description of this section: in the conventional technology, the coating is usually applied by means of brushing, roller coating, airless spraying and the like. The technical difficulty of the patent is that the micro-nano size of the lubricating oil droplets is kept in the coating process of the coating, the lubricating oil droplets are not fused with each other to increase the volume, and the uniform distribution degree of the lubricating oil droplets is kept. Compared with the means of brushing, roller coating, airless spraying and the like, the method for coating the fluorine-containing self-polishing resin-based ultra-smooth coating by adopting a dip coating method more effectively maintains the micro-nano size and distribution of small lubricating oil droplets in the resin after ultrasonic treatment, so that the prepared coating can slow down the loss of the lubricating oil to a great extent;

meanwhile, the thickness of the coating is an important index for determining the service life of the coating and the comprehensive performance of the coated equipment. It is well known that the service life of a self-polishing coating is proportional to the thickness of the coating. The resin matrix of this patent is from polishing resin, and the coating thickness is thicker, and the life of coating is longer, and when coating thickness exceeded 180 mu m, can seriously influence the mobility of equipment such as yacht, naval vessel, caused the speed to descend. Thus allowing a longer service life of the coating and ensuring the basic performance of the coated equipment when the coating thickness is kept at 180 μm.

(5) The fluorine-containing acrylate monomer is hexafluorobutyl methacrylate.

Technical description of this section: the self-polishing rate of the resin matrix of the coating determines the service life of the coating, so that the regulation of the self-polishing rate of the resin matrix is also one of the technical difficulties of the invention. The self-polishing rate of the synthetic resin is adjusted by the side chains with different lengths of the fluorine-containing acrylate monomer. When a fluorine-containing acrylate monomer with a longer side chain is selected, such as dodecafluoroheptyl methacrylate, the steric hindrance effect caused by the longer side chain can reduce the grafting rate of the pyridine triphenylborane, thereby influencing the self-polishing rate and the antifouling property of the coating. When a fluoroacrylate monomer having a shorter side chain is selected, such as trifluoroethyl methacrylate, the hydrophobic region of the coating matrix is relatively small, the self-polishing rate is fast, and the coating life is short. Therefore, the hexafluorobutyl methacrylate with moderate fluorine-containing side chain is selected to prepare the coating resin matrix, so that the coating has long service life.

(6) The carboxyl-containing acrylic monomer is acrylic acid.

Technical description of this section: compared with other acrylic monomers such as methacrylic acid and the like, the acrylic acid has the lowest glass transition temperature of 106 ℃, and the addition amount range is wider according to the fox formula, so that the self-polishing rate of the resin is easier to regulate, and the coating has longer service life.

(7) The acid value of the synthetic resin product a is 80-120 mgKOH/g.

Technical description of this section: as the resin matrix is polished layer by layer, the lubricating oil in the resin matrix is gradually exposed to the surface of the renewed coating and then is lost. Therefore, the polishing rate of the resin matrix of the coating is controlled, the service life of the coating can be prolonged, and the loss of lubricating oil can be reduced. The acid value of the conventional self-polishing resin is 90-400 mgKOH/g, and the acid value of the resin is controlled to be 80-120 mgKOH/g by adjusting the adding amount of the acrylic monomer, so that the self-polishing rate of the coating resin matrix and the lubricating oil loss rate are reduced on the basis of ensuring that the self-polishing speed can desorb attached fouling organisms.

(8) The addition amount of the perfluoropolyether lubricating oil is 1-9 wt%.

Technical description of this section: the addition of the lubricating oil is a key factor of the coating lubricating oil exudation rate and the coating self-repairing speed. When the addition amount of the perfluoropolyether lubricating oil is 1-9 wt%, the prepared super-smooth coating has high self-repairing speed, lubricating oil seepage rate and good sagging property. When the addition of the lubricating oil is less than 1 wt%, the self-repairing speed at normal temperature exceeds 10 hours, and the coating cannot be rapidly repaired; when the addition amount of the lubricating oil is more than 9 wt%, the coating has obvious sagging performance at normal temperature and cannot meet the normal use.

(9) The fluorine-containing silane coupling agent is heptadecafluorodecyltrimethoxysilane.

Technical description of this section: the fluorine-containing coating in the conventional technology has low surface energy because of the fluorine-containing functional group in the coating, so that the coating has weak adhesion on a substrate and is easy to fall off. How to improve the adhesion of the coating on the substrate is also one of the technical difficulties of the patent. Compared with other silane coupling agents, the heptadecafluorodecyltrimethoxysilane has longer fluorine-containing side chains, can form stronger intermolecular acting force with fluorine-containing acrylic acid self-polishing resin of a coating resin matrix and C-F bonds in perfluoropolyether lubricating oil, shows stronger bonding force macroscopically, and enhances the adhesive force of the super-smooth coating and a substrate.

(10) The temperature range of the coating airing is 20-40 ℃.

Technical description of this section: within the temperature range, the super-smooth coating can be quickly dried on the premise of less volatilization of lubricating oil. When the temperature is lower than 20 ℃, the time for airing the ultra-smooth coating to the constant weight is longer, and is more than 24 hours. When the temperature is higher than 45 ℃, the volatilization loss of the lubricating oil can be caused, so that the service life of the super-smooth coating is shortened.

Compared with the prior art, the self-repairing super-smooth acrylic acid fluoroboron coating is prepared by ultrasonically mixing the lubricating oil and the acrylic acid fluoroboron self-polishing resin and dip-coating the mixture, so that the preparation steps are simplified, the preparation time is shortened, the lubricating oil exists in the coating in the form of micro-nano droplets, the contact with the outside is reduced, the consumption of the lubricating oil is reduced, and the service life of the coating is prolonged. The coating form of the self-polishing resin coated lubricating oil endows the coating with self-repairing capability, so that the coating can still be used through self-repairing when the coating is damaged, the frequency of equipment maintenance using the coating is reduced, and manpower and material resources are saved. The base resin adopts the acrylic acid fluorine type of having concurrently low surface energy and polishing effect from polishing resin base member, and the polishing effect constantly takes place for the resin base member, guarantees the invariable seepage rate of lubricating oil, and the porous substrate is changeed and adheres to the problem of stained living beings after the super-slip coating lubricating oil consumption is totally solved from the polishing effect of resin base member simultaneously, makes the coating still have certain antifouling performance in the change stage.

Drawings

FIG. 1 is a polarized microscope photograph and cross-sectional photograph of various fluorine boron acrylate self-healing super-slip coatings, wherein: a. SABFP-1; b. SABFP-2; c. SABFP-3; d. SABFP-4; e. SABFP-5; f. an ABFP cross-sectional view; g. SABFP-1; h. SABFP-2; i. SABFP-3; j. SABFP-4; k. SABFP-5; l, light transmittance.

FIG. 2 shows the failure time of the self-repairing super-smooth coating of the acrylic acid fluorine boron: b. 0 min; c. 20 min; d. 40 min; e. 60 min; f. the surface topography after 80min (SABFP-5,20 ℃), and a, is the topography before destruction.

FIG. 3 shows the fouling and adhesion conditions of the surface of different fluorine-boron acrylate self-repairing super-smooth coatings after a control group and a blank group are soaked in a Bohai sea area of a Bohai sea for 60 days.

Detailed Description

The invention is described in more detail below by way of example.

Examples 1

a. Preparation of resin matrix: dropping a mixed solution of 20g of hexafluorobutyl methacrylate, 40g of methacrylic acid, 10g of methyl methacrylate and 25g of butyl acrylate into 120g of dimethylbenzene at the temperature of 80 ℃ for 6 hours, then, subsequently, dropping a mixed solution of 1g of benzoyl peroxide and 20g of dimethylbenzene for 30 minutes, and continuing to react for 90 minutes after the dropping is finished to obtain the fluorine-containing acrylic resin (product a).

b. 100g of a fluorine-containing acrylic resin (product a) and 9.8g of pyridine triphenylborane were added to 75g of xylene and reacted at 90 ℃ for 4 hours to obtain a fluorine-containing acrylic boron resin (product b) having an acid value of 100 mgKOH/g.

c. Wiping the glass slide with absolute ethyl alcohol, removing oil stains and other impurities on the surface, drying by air blowing at 80 ℃, soaking in 20mL of 5% by volume of an ethanol solution containing a fluorine-containing silane coupling agent for 120min, taking out, and drying to constant weight under a nitrogen atmosphere at 35 ℃.

d. 0.2g of perfluoropolyether lubricating oil was weighed and added to 19.8g of an acrylic acid fluoroboric resin (product b), and ultrasonic dispersion treatment was carried out for 180 seconds to predisperse the perfluoropolyether lubricating oil in the resin.

e. A super-slip coating having a dry film thickness of about 180 μm was dip-coated on the treated substrate by dip coating, the coating was placed horizontally and the coating was air-dried at 40 ℃.

Self-polishing rate: 0.5mg · m^-2·d^-1

Attachment rate of nitzschia closterium: 2.1 percent.

EXAMPLES example 2

The perfluoropolyether lube oil was added in an amount of 0.6g, and the mass of acrylic acid fluoroborate resin (product b) was 19.4g, with the remainder being unchanged, as shown in example 1.

Self-polishing rate: 0.6mg · m^-2·d^-1

Attachment rate of nitzschia closterium: 2.0 percent.

EXAMPLE 3

The amount of perfluoropolyether lube added was 1g and the mass of acrylic acid fluoroboric resin (product b) was 19g, the rest of the process being unchanged, as shown in example 1.

Self-polishing rate: 0.5mg · m^-2·d^-1

Attachment rate of nitzschia closterium: 1.6 percent.

EXAMPLE 4

The perfluoropolyether lube oil was added in an amount of 1.4g, the mass of acrylic acid fluoroborate resin (product b) was 18.6g, and the rest of the process was unchanged as shown in example 1.

Self-polishing rate: 0.7mg · m^-2·d^-1

Attachment rate of nitzschia closterium: 1.3 percent.

EXAMPLE 5

The perfluoropolyether lube oil was added in an amount of 1.8g, the mass of acrylic acid fluoroborate resin (product b) was 18.2g, and the rest of the process was unchanged as shown in example 1.

Self-polishing rate: 0.8mg · m^-2·d^-1

Attachment rate of nitzschia closterium: 1.5 percent.