Preparation method and application of acrylic acid modified maleic acid dihydroxy silicone oil resin

Abstract

The invention discloses acrylic acid modified maleic acid dihydroxyl silicone grease resin and a preparation method thereof, and further utilizes the acrylic acid modified maleic acid dihydroxyl silicone grease resin to prepare a micro-nano self-wrinkling hydrogel organosilicon antifouling coating. In the acrylic acid modified maleic acid dihydroxyl silicone oil resin synthesized by the invention, due to the hydrophobicity of silicon methyl and the hydrophilicity of hydroxyl, a surface of which the roots repel each other and the top ends are hydrophilic and which stretches in water to form micro-nano self-wrinkles is formed in water, and the acrylic acid modified maleic acid dihydroxyl silicone oil resin has a lotus leaf villus effect, is not easily wetted and adsorbed by marine organisms, and has a good anti-wrinkling effect even if a small amount of silicone oil is adsorbed. Due to the fact that a foundation adsorbed on the surface of the micro-nano self-wrinkles is not firm, the micro-nano self-wrinkles are easily desorbed under the action of shearing force when a ship starts, meanwhile, the friction resistance of the surface of the micro-nano self-wrinkles is greatly reduced, the resistance is reduced by 12-15% in a ship navigation test, the energy consumption is reduced by about 12-15%, and huge economic benefits are generated.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of ship antifouling coatings, and particularly relates to preparation of acrylic acid modified maleic acid dihydroxy silicone oil resin and preparation and application of the resin in micro-nano self-pleated hydrogel silicone antifouling coating. BACKGROUND

[0002] The silicone hydrogel antifouling coating is generally free of biocides or contains a small amount of biocides, belongs to environmentally friendly ship antifouling coatings, and moreover, the hydrogel immersed in water forms a lotus-like micro-nano self-pleated hydrogel surface due to the hydrophilicity of hydroxyl groups and the hydrophobicity of silicon, water cannot be wetted, and is not easy to be adsorbed by marine organisms, thereby greatly reducing the ship sailing resistance and having the green sailing energy-saving effect.

[0003] At present, foreign capital silicone antifouling coatings use hydroxyl silicone oil micro-nano self-pleated hydrogel silicone coating, and due to a large number of silicon methyl groups at the root, the low surface energy of the silicon methyl groups, and the poor interlayer adhesion, the coating is very easy to fall off and is torn off by a small scratch. The coating of the hydroxyl silicone oil micro-nano self-pleated hydrogel technology is very soft and has low tensile strength and is very easy to tear. The construction of the hydroxyl silicone oil micro-nano self-pleated hydrogel silicone antifouling coating developed by foreign capital enterprises is difficult, and the requirements for the environment are harsh. The curing of the coating of the hydroxyl silicone oil micro-nano self-pleated hydrogel technology only has hydrolysis and condensation curing of hydroxyl silicone oil and polyether modified silane, and the requirements for the humidity, temperature and wind speed of the environment are very high. SUMMARY

[0004] The application aims at solving the problems of the prior art, and provides a maleic acid dihydroxy silicone oil resin modified by acrylic acid and a preparation method thereof.

[0005] The application further aims to solve the technical problem of preparing a micro-nano self-pleated hydrogel silicone antifouling coating by using the maleic acid dihydroxy silicone oil resin modified by acrylic acid.

[0006] In order to solve the above technical problems, the application discloses a preparation method of maleic acid hydroxyl silicone oil monoester, which is prepared by ring-opening reaction of hydroxyl silicone oil and maleic anhydride according to the following reaction: , wherein n is an integer of 2-8.

[0007] Specifically, the hydroxyl silicone oil is put into a reaction kettle, stirring is started, the maleic anhydride is then put into the reaction kettle, nitrogen gas is introduced as a protective gas, heating and temperature rising are performed to 55-60 DEG C, and heat preservation is performed for 2-4 hours to obtain the maleic acid hydroxyl silicone oil monoester. In an embodiment, heating and temperature rising are performed to 58 DEG C by introducing nitrogen gas as a protective gas, heat preservation is performed for 3 hours to obtain the maleic acid hydroxyl silicone oil monoester. The molar ratio of the hydroxyl silicone oil to the maleic anhydride is 1:1.

[0008] The application further provides a preparation method of the maleic acid dihydroxyl silicone oil ester, which comprises the following steps: reacting hydroxyl silicone oil and the maleic acid hydroxyl silicone oil monoester under the action of a catalyst. , In the formula, n is an integer of 2-8.

[0009] Specifically, the maleic acid hydroxyl silicone oil monoester and the hydroxyl silicone oil are put into a reaction kettle, then a reaction catalyst dodecanoic acid and xylene are added, stirring is started, nitrogen is introduced, heating is performed until the xylene reflux temperature is reached, the xylene starts to reflux and dehydrate, and the process is continued until no water is dehydrated, and then the maleic acid dihydroxyl silicone oil ester is obtained by cooling. The molar ratio of the hydroxyl silicone oil to the maleic acid hydroxyl silicone oil monoester is 1:1, optionally, the reaction catalyst is dodecanoic acid, and the amount of the dodecanoic acid is 1%-2% of the mass of the reactants; the amount of the xylene is 1%-2% of the mass of the reactants. Generally, the xylene reflux temperature is 138±2°C. In some specific embodiments, heating is performed until the xylene starts to reflux and dehydrate at 138°C.

[0010] Further, the application further provides an acrylic modified maleic acid dihydroxyl silicone oil resin, which comprises the following components in the following weight fractions: 49-56 parts of the maleic acid dihydroxyl silicone oil ester, 1-8 parts of methyl methacrylate, 0.6-1.2 parts of tert-butyl peroxybenzoate, and 28-32 parts of xylene.

[0011] The application further provides a preparation method of the acrylic modified maleic acid dihydroxyl silicone oil resin, which comprises the following steps: (1) the formula amount of the maleic acid dihydroxyl silicone oil ester, methyl methacrylate, styrene and butyl acrylate is weighed, 0.8%-1.2% of the mass of the monomers of tert-butyl peroxybenzoate is uniformly stirred, and then poured into a high tank, (2) 90-95 wt of the formula amount of xylene is added into a reaction kettle, and when the temperature of the xylene is increased to the xylene reflux temperature, reflux is started, and nitrogen is introduced into the reaction kettle with refluxing xylene, (3) the mixed monomers in the high tank are added dropwise into the reaction kettle with refluxing, the dropwise addition is uniformly completed, and refluxing is maintained for 1-2 hours; preferably, the dropwise addition is uniformly completed for 3 hours, (4) another part of tert-butyl peroxybenzoate and another part of xylene are added into the reaction kettle, and the mixture is maintained for 2-3 hours; (5) heating is stopped, and the acrylic modified maleic acid dihydroxyl silicone oil resin is obtained by cooling.

[0012] The application further provides an application of the acrylic modified maleic acid dihydroxyl silicone oil resin in preparing a silicone antifouling coating.

[0013] The application further provides a micro-nano self-pleated hydrogel silicone antifouling paint, which comprises the following components in weight fractions: 80-90 parts of acrylic acid modified maleic dihydroxy silicone oil resin, 1-5 parts of anti-settling agent, 4-8 parts of pigment powder, and 4-8 parts of xylene.

[0014] In some embodiments, the anti-settling agent is polyamide wax paste, and / or the pigment powder is any one of iron black powder, iron red powder, phthalocyanine blue, titanium white powder, or permanent red.

[0015] In a specific embodiment, the micro-nano self-pleated hydrogel silicone antifouling paint comprises 86 parts of acrylic acid modified maleic dihydroxy silicone oil resin, 2 parts of anti-settling agent (polyamide wax paste), 6 parts of pigment powder, and 6 parts of xylene.

[0016] The application further provides a preparation method of the above micro-nano self-pleated hydrogel silicone antifouling paint, comprising the following steps: (1) adding the acrylic acid modified maleic dihydroxy silicone oil resin into a cylinder; (2) adding the anti-settling agent while stirring, and dispersing for 10-20 minutes; (3) adding the pigment powder while stirring, and dispersing until the fineness is less than 30 microns; preferably, the stirring rate is 1000-1300 revolutions per minute; (4) adding xylene and stirring uniformly to obtain the acrylic acid modified maleic dihydroxy silicone oil resin micro-nano self-pleated hydrogel silicone antifouling paint.

[0017] Advantages: compared with the prior art, the application has the following advantages: (1) the acrylic acid modified maleic dihydroxy silicone oil resin prepared by the application and the micro-nano self-pleated hydrogel silicone antifouling paint prepared by further using the acrylic acid modified maleic dihydroxy silicone oil resin have two aspects in the film curing: firstly, the thermoplastic volatilization curing of the acrylic acid part is fast and has low requirements on the environment; secondly, the hydrolysis curing of the hydroxy silicone oil and the polyether modified silane, thus reducing the construction difficulty.

[0018] (2) in the synthesized acrylic acid modified maleic dihydroxy silicone oil resin, due to the hydrophobicity of the silicon methyl and the hydrophilicity of the hydroxyl, the root part repels each other and the top part is hydrophilic in water, and the micro-nano self-pleated surface is formed in water, which has the lotus hair effect and is not easy to be wetted and adsorbed by marine organisms; even if a small amount of adsorption occurs, the root base adsorbed by the micro-nano self-pleated surface is not firm, and the ship is easy to be desorbed under the action of shearing force.

[0019] (3) the frictional resistance of the micro-nano self-pleated surface is greatly reduced, the resistance is reduced by 12-15% in the ship sailing test, the energy consumption is reduced by about 12-15%, and great economic benefits are generated. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 Photos of the sample plates after painting and before being immersed in the sea, wherein Nos. 1-4 correspond to the sample plates after painting with the coatings of Examples 1-4, respectively; Figure 2 Photos of the sample plates after painting and after being immersed in the sea for 1 year, wherein Nos. 1-4 correspond to the sample plates after painting with the coatings of Examples 1-4, respectively. DETAILED DESCRIPTION

[0021] The above and / or other aspects of the present application will become apparent and more readily appreciated from the following description, taken in conjunction with the accompanying drawings, in which:

[0022] In the following examples, the maleic acid dihydroxyl silicone oil ester is prepared by the following method: (1) 1 mole of maleic anhydride (maleic anhydride) and 1 mole of hydroxyl silicone oil with a viscosity of 300 mpa.s are mixed, and under the measures of passing protective gas nitrogen and stirring (80-120 rpm), the temperature is raised to 58°C, and kept for 3 hours to generate maleic acid hydroxyl silicone oil monoester, and then cooled down;

[0023] (2) The maleic acid hydroxyl silicone oil monoester obtained in step 1 and hydroxyl silicone oil with a viscosity of 300 mpa.s are mixed in a molar ratio of 1:1, and then 1% of the reaction mass of dodecanoic acid (reaction catalyst) and 2% of the reaction mass of a small amount of refluxing dehydrating agent xylene are added, and protective gas nitrogen is passed, and stirring and heating are performed to raise the temperature to 138°C, and xylene begins to reflux and dehydrate until 1 mole of water is removed, and then cooled to obtain maleic acid dihydroxyl silicone oil ester. EXAMPLE

[0024] The maleic acid dihydroxyl silicone oil ester 56 parts, methyl methacrylate 5 parts, styrene 5 parts, butyl acrylate 4 parts, and tert-butyl benzene peroxide 0.7 parts are poured into a high tank and stirred uniformly. Dodecane 28 parts are put into a reaction kettle, nitrogen is passed into the reaction kettle, and when the temperature is raised to 138°C, refluxing is started, and the mixed monomers in the high tank are added dropwise into the reaction kettle, and the dropping is completed uniformly in 3 hours, and after the dropping is completed, refluxing and heat preservation are performed for 1 hour. Tert-butyl benzene peroxide 0.1 part and xylene 2 parts are added into the reaction kettle, and heat preservation is performed for 2 hours. The heating is stopped, and the acrylic acid modified maleic acid dihydroxyl silicone oil resin is obtained after cooling.

[0025] The acrylic acid modified maleic acid dihydroxyl silicone oil resin 86 parts and anti-settling agent (polyamide wax slurry) 2 parts are put into a drawing cylinder, and dispersed at a high speed of 1200 rpm for 15 minutes, and then iron black powder 6 parts is added, and dispersed at a high speed until the fineness is less than 30 microns, and then xylene 6 parts is added, and the acrylic acid modified maleic acid dihydroxyl silicone oil resin micro-nano self-pleated hydrogel organic silicon antifouling paint is obtained after filtration and packaging. Example

[0026] Maleic acid dihydroxy silicone oil ester 50 parts, methyl methacrylate 8 parts, styrene 6 parts, butyl acrylate 6 parts, and t-butyl peroxy benzoate 0.7 parts were poured into a high tank and stirred uniformly. Dicyclic hydrocarbon 28 parts was put into a reaction kettle, and nitrogen was introduced into the reaction kettle to stir and heat to 138°C to start refluxing. The mixed monomers in the high tank were added dropwise into the reaction kettle, and the dropping was completed uniformly in 3 hours. After the dropping was completed, refluxing and heat preservation were carried out for 1 hour. T-butyl peroxy benzoate 0.1 part and dicyclic hydrocarbon 2 parts were added into the reaction kettle, and heat preservation was carried out for 2 hours. The heating was stopped, and acrylic acid modified maleic acid dihydroxy silicone oil resin was obtained by cooling.

[0027] Maleic acid dihydroxy silicone oil resin 86 parts and anti-settling agent (polyamide wax slurry) 2 parts were put into a pull tank and high-speed dispersed for 15 minutes. Iron red powder 6 parts was added and high-speed dispersed until the fineness was less than 30 microns. Dicyclic hydrocarbon 6 parts was added, and the micro-nano self-pleated hydrogel silicone antifouling paint prepared from the acrylic acid modified maleic acid dihydroxy silicone oil resin was obtained by filtering and packaging. Example

[0028] Maleic acid dihydroxy silicone oil ester 56 parts, methyl methacrylate 6 parts, styrene 6 parts, butyl acrylate 2 parts, and t-butyl peroxy benzoate 0.7 parts were poured into a high tank and stirred uniformly. Dicyclic hydrocarbon 28 parts was put into a reaction kettle, and nitrogen was introduced into the reaction kettle to stir and heat to 138°C to start refluxing. The mixed monomers in the high tank were added dropwise into the reaction kettle, and the dropping was completed uniformly in 3 hours. After the dropping was completed, refluxing and heat preservation were carried out for 1 hour. T-butyl peroxy benzoate 0.1 part and dicyclic hydrocarbon 2 parts were added into the reaction kettle, and heat preservation was carried out for 2 hours. The heating was stopped, and acrylic acid modified maleic acid dihydroxy silicone oil resin was obtained by cooling.

[0029] Maleic acid dihydroxy silicone oil resin 86 parts and anti-settling agent (polyamide wax slurry) 2 parts were put into a pull tank and high-speed dispersed for 15 minutes. Iron red powder 6 parts was added and high-speed dispersed until the fineness was less than 30 microns. Dicyclic hydrocarbon 6 parts was added, and the micro-nano self-pleated hydrogel silicone antifouling paint prepared from the acrylic acid modified maleic acid dihydroxy silicone oil resin was obtained by filtering and packaging. Example

[0030] Put maleic acid dihydroxy silicone oil ester 52 parts, methyl methacrylate 8 parts, styrene 6 parts, butyl acrylate 4 parts, and tert-butyl benzene peroxide 0.7 parts into a high tank and stir to be uniform. Put dimethylbenzene 28 parts into a reaction kettle, and stir to be uniform. When the temperature is raised to 138°C, start refluxing, and keep refluxing. Drop the mixed monomers in the high tank into the reaction kettle, and drop uniformly for 3 hours. After dropping, keep refluxing for 1 hour. Add tert-butyl benzene peroxide 0.1 part and dimethylbenzene 2 parts into the reaction kettle, and keep for 2 hours. Stop heating, and cool to obtain an acrylic acid modified maleic acid dihydroxy silicone oil resin.

[0031] Put the acrylic acid modified maleic acid dihydroxy silicone oil resin 86 parts and anti-settling agent (polyamide wax slurry) 2 parts into a cylinder, and high-speed disperse for 15 minutes. Then put phthalocyanine blue 3 parts and titanium dioxide 3 parts into the cylinder, and high-speed disperse until the fineness is less than 30 microns. Then put dimethylbenzene 6 parts into the cylinder, filter, and package to obtain an acrylic acid modified maleic acid dihydroxy silicone oil resin micro-nano self-pleated hydrogel organic silicon antifouling paint.

[0032] The organic silicon antifouling paint is made into a sample plate for testing.

[0033] The sample plate is sandblasted to reach Sa2 level. Spray an epoxy universal primer on the sandblasted sample plate, and control the dry film thickness to be 100±10 um. After drying for 24 hours, spray the organic silicon connecting paint, and control the dry film thickness to be 90±10 um. After drying for 24 hours, spray the organic silicon antifouling paint of examples 1-4 and foreign competitive products, and control the dry film thickness to be 100±10 um. After the sample plate is maintained at 25°C for 7 days, test is performed.

[0034] Table 1

[0035] From the test results in the above table, it can be seen that the adhesion and tensile strength of the micro-nano self-pleated hydrogel organic silicon antifouling paint prepared by the acrylic acid modified maleic acid dihydroxy oil resin are significantly improved, and the service life of the organic silicon antifouling paint is improved.

[0036] To test the effect of the listed organic silicon antifouling paint in seawater, the sample plate is hung in the sea of Xiamen 725 for one year, and the results are shown in Figure 1 and Figure 2 No marine organisms are attached, which indicates that the micro-nano self-pleated surface formed by the micro-nano self-pleated hydrogel organic silicon antifouling paint prepared by the acrylic acid modified maleic acid dihydroxy silicone oil resin has the lotus down effect, is not easy to be adsorbed by marine organisms, and has good antifouling effect.

[0037] The application provides a preparation idea and method of acrylic modified maleic acid dihydroxy linseed resin. The method and approach for specifically realizing the technical scheme are various, and the above description is only the preferred embodiment of the application. It should be pointed out that, for ordinary skilled in the art, some improvements and refinements can be made without departing from the principle of the application, and these improvements and refinements should also be regarded as the protection scope of the application. The components not explicitly described in the embodiment can be realized by the prior art.

Claims

1. A method for producing a hydroxysilicone monoester of maleic acid, characterized by, The hydroxyl silicone oil is subjected to ring-opening reaction with maleic anhydride according to the following reaction to obtain: ， wherein n is an integer of 2-8.

2. The production method according to claim 1, characterized by, The hydroxyl silicone oil is put into a reaction kettle, stirring is started, then the maleic anhydride is put into the reaction kettle, nitrogen gas is introduced for protection, and heating is started until the temperature reaches 55-60℃, and the temperature is kept for 2-4 hours to obtain the maleic anhydride hydroxyl silicone oil monoester.

3. A method for preparing a maleic acid dihydroxyl silicone oil ester, characterized by, The maleic anhydride hydroxyl silicone oil monoester is reacted with the hydroxyl silicone oil under the action of a catalyst to obtain: ， wherein n is an integer of 2-8.

4. The production method according to claim 3, characterized by, The maleic anhydride hydroxyl silicone oil monoester and the hydroxyl silicone oil are put into a reaction kettle, then the reaction catalyst dodecanoic acid and xylene are added, stirring is started, nitrogen gas is introduced, heating is started until the temperature reaches the refluxing temperature of xylene, xylene starts to reflux and dehydrate until no water is dehydrated, and then the temperature is cooled to obtain the maleic anhydride dihydroxyl silicone oil ester.

5. An acrylic-modified maleic dihydroxy silicone oil resin, characterized by comprising: The components include the following weight fractions: The maleic anhydride dihydroxyl silicone oil ester is prepared by the preparation method of claim 3 and / or 4.

6. The method of making an acrylic-modified maleic dihydroxysilicone oil resin of claim 5, characterized in that, The method comprises the following steps: (1) The formula amount of the maleic anhydride dihydroxyl silicone oil ester, methyl methacrylate, styrene, and butyl acrylate is weighed, and 0.8%-1.2% of the mass of the monomers of the peroxide tert-butyl benzoate is stirred uniformly and poured into a high tank, (2) 90-95wt of the formula amount of xylene is added to a reaction kettle, and stirring is started, and the temperature is increased until the xylene starts to reflux at the refluxing temperature of xylene, and then nitrogen gas is introduced into the reaction kettle with refluxing xylene, (3) The refluxing is kept, and the mixed monomers in the high tank are added dropwise into the reaction kettle, and the dropwise addition is kept until the dropwise addition is completed, and then the refluxing is kept for 1-2 hours; (4) Another part of the peroxide tert-butyl benzoate and another part of xylene are added to the reaction kettle, and the temperature is kept for 2-3 hours; (5) The heating is stopped, and the temperature is cooled to obtain the acrylic modified maleic anhydride dihydroxyl silicone oil resin.

7. The use of the acrylic modified maleic anhydride dihydroxyl silicone oil resin of claim 5 in preparing a silicone antifouling coating.

8. A micro- and nanometer self-creped hydrogel silicone antifouling paint, characterized by, The components include the following weight fractions: 80-90 parts of the acrylic modified maleic anhydride dihydroxyl silicone oil resin, 1-5 parts of an anti-settling agent, 4-8 parts of pigment powder, and 4-8 parts of xylene.

9. The micro-nano self-wrinkled hydrogel silicone antifouling coating according to claim 8, characterized in that, The anti-settling agent is polyamide wax paste, and / or the pigment powder is any one of iron black powder, iron red powder, phthalocyanine blue, titanium white powder, or permanent red.

10. The method for preparing the micro-nano self-pleated hydrogel organosilicon antifouling coating according to claim 8 or 9, characterized in that, The method comprises the following steps: (1) The acrylic modified maleic anhydride dihydroxyl silicone oil resin of claim 5 is added into a draw cylinder, (2) The anti-settling agent is added while stirring, and the dispersion is kept for 10-20 minutes, (3) The pigment powder is added while stirring, and the dispersion is kept until the fineness is less than 30 microns, (4) Xylene is added and stirred uniformly to obtain the acrylic modified maleic anhydride dihydroxyl silicone oil resin micro-nano self-pleated hydrogel silicone antifouling coating.

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