A method for preparing polar ocean antifouling resin

Abstract

The invention discloses a method for preparing a polar ocean antifouling resin, firstly preparing an antifouling monomer with antifouling activity by reacting a chlorinated isothiazolinone fungicide with acrylic acid, and then reacting the monomer with vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate to synthesize an acrylic silane isothiazolinone polar antifouling resin. The isothiazolinone side chain unit on the resin molecular structure synthesized by the method can provide excellent antifouling performance for the antifouling resin, thereby reducing the use of antifouling agents and effectively protecting the fragile polar ocean ecological environment; the Si-O-Si soft segment and the adjustable glass transition temperature can effectively reduce the low-temperature brittleness, ice adhesion and adhesion of fouling organisms of the resin, thereby giving the resin good antifouling and low-temperature resistance.

Description

Technical Field

[0001] The invention belongs to the field of special resin preparation, and in particular relates to a method for preparing a marine antifouling resin that can be used under severe polar conditions. Background Art

[0002] The polar regions have always been regarded as important strategic areas by various countries due to their rich natural resources and potential convenient shipping routes. Therefore, polar ships and shipping will have great strategic and economic value in the future. In polar oceans, the surface of ships will still be attached by marine fouling organisms. In addition to increasing navigation resistance, fouling organisms will also cause pitting corrosion on the hull, seriously endangering the safety of life and property of crew members. One of the most effective ways to prevent marine organisms from attaching is to apply marine antifouling paint.

[0003] Yang Bin from Chongqing University synthesized a fluorine-modified acrylic resin. When the dosage of perfluorooctane methacrylate is 5%, the adhesion between the resin coating and ice can be reduced by nearly 80%, which plays an anti-icing role. At the same time, its low surface energy surface can also reduce the adhesion between the resin coating and fouling organisms, and has a certain anti-fouling effect. However, the glass transition temperature of its synthetic resin is between 30-80℃. It is in a glassy state under the low temperature environment of the polar regions, and it is very brittle. It is easy for the coating to be damaged and lose its protective effect. Chen Kaifeng from the Xiamen Materials Research Institute of the 725th Institute of China Shipbuilding Industry Corporation used epoxy resin, butyl acetate and isocyanate-terminated polyurethane to synthesize a wear-resistant and impact-resistant polyurethane toughened epoxy resin for polar regions. However, the resin structure does not have anti-fouling active groups and cannot prevent the attachment of fouling organisms.

[0004] There are very few reports on the research of polar antifouling resins at home and abroad. This is mainly because in the extreme polar service environment, the resin matrix of the antifouling coating will face the following severe challenges and difficulties due to the low temperature and special marine environment:

[0005] 1. The antifouling resin matrix will become more brittle and its mechanical strength will decrease at extremely low temperatures in polar regions, which can easily cause damage to the antifouling coating and reduce its protective ability.

[0006] 2. The hull resin coating will be hit by ice and rubbed by floating ice in the polar marine environment. It is difficult for the resin matrix to have both high toughness and friction resistance.

[0007] 3. Traditional self-polishing antifouling resins will release small molecular side chains into the marine environment during the self-polishing process, damaging the ecological environment.

[0008] Traditional self-polishing antifouling resins do not have antifouling activity and require the addition of a large amount of antifouling agents to achieve an antifouling effect. However, the use of a large amount of antifouling agents can also cause damage to the marine ecological environment. Summary of the invention

[0009] The object of the present invention is to provide a method for preparing a marine antifouling resin which can be used under severe polar conditions.

[0010] To achieve the above-mentioned object of the invention, the preparation method of the polar ocean antifouling resin provided by the present invention comprises the following steps:

[0011] (1) reacting a chlorine-containing isothiazolinone fungicide with acrylic acid under the catalysis of triethylamine, and obtaining an acrylic isothiazolinone antifouling monomer after the reaction is completed;

[0012] (2) The polar marine antifouling resin is obtained by randomly or block polymerizing acrylic silane isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate to form acrylic silane isothiazolinone.

[0013] The preparation method of polar ocean antifouling resin comprises the following specific steps:

[0014] (1) adding a chlorine-containing isothiazolinone fungicide and triethylamine to propylene glycol methyl ether, raising the temperature to 90-100° C., and then dropping a mixture of acrylic acid and deionized water. After the dropping is completed, the reaction is continued until the reaction is complete. After the reaction is completed, a liquid product containing acrylic acid isothiazolinone antifouling monomer is obtained;

[0015] (2) A liquid product containing acrylic isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate are mixed to form a mixed monomer; propylene glycol methyl ether and xylene are mixed and heated to 90-100° C., and the mixed monomer is added dropwise under nitrogen protection. After the addition is completed, a xylene solution of benzoyl peroxide is added to continue the reaction. After the reaction is completed, a polar marine antifouling resin is obtained.

[0016] In the step (1), the mass ratio of acrylic acid to chlorinated isothiazolinone fungicide is 1:1-5; the amount of triethylamine used is 0.75-3 times the mass of acrylic acid; the mass ratio of acrylic acid to deionized water is 1:1-3; and the amount of propylene glycol methyl ether used is 6-9 times the weight of acrylic acid.

[0017] In the step (2), the mass ratio of the liquid product containing acrylic isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate is 5-50:5-45:10-25:5-30; the amount of propylene glycol methyl ether is 6-8% of the weight of the mixed monomers, and the amount of xylene is 23-32% of the weight of the mixed monomers; the amount of benzoyl peroxide xylene solution is 0.9-1.6 times the mass of butyl acrylate, and the mass ratio of benzoyl peroxide to xylene in the benzoyl peroxide xylene solution is 1:12-25.

[0018] In the step (2), the dropwise addition of the mixed monomers and / or the subsequent reaction after the dropwise addition is carried out under magnetic stirring at a stirring speed of 600 rpm.

[0019] In the step (1), the time for adding the mixture of acrylic acid and deionized water is 1.5-3 hours, and the time for continuing the reaction after the addition is 4-6 hours.

[0020] In the step (2), the dropwise addition time of the mixed monomer is 3-10 hours, and the reaction time after the addition of the xylene solution of benzoyl peroxide is 1-4 hours.

[0021] The chlorine-containing isothiazolinone fungicide is 5-chloro-2-methyl-4-isothiazoline-3-one or 4,5-dichloro-N-octyl-4-isothiazoline-3-one; preferably 4,5-dichloro-N-octyl-4-isothiazoline-3-one.

[0022] The weight average molecular weight of the vinyl polydimethylsiloxane is 1000-5000.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] 1. Introducing isothiazolinone side chains with antifouling activity into the resin molecular structure can reduce the use of toxic antifouling agents, and the small molecular side chains of the resin will not be released into the ocean during use, effectively protecting the fragile polar marine ecological environment;

[0025] 2. The bifunctional acrylic isothiazolinone antifouling monomer and vinyl polydimethylsiloxane monomer form an interpenetrating cross-linked network during the polymerization process, which enhances the resin's anti-floating ice impact strength;

[0026] 3. The Si-O-Si soft segment of vinyl polydimethylsiloxane, butyl acrylate with extremely low glass transition temperature and 2-ethylhexyl acrylate make the synthesized antifouling resin still in a highly elastic state at extremely low temperatures and have a certain degree of flexibility;

[0027] 4. The bactericidal function provided by the isothiazolinone side chain of the resin and the low surface energy anti-biological adhesion effect provided by vinyl polydimethylsiloxane effectively ensure the anti-fouling performance of the resin in polar environments. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below by way of examples, which are not intended to limit the scope of the present invention.

[0029] Implementation Example 1

[0030] Weigh 28.2 g of 4,5-dichloro-N-octyl-4-isothiazolin-3-one and 9.5 g of triethylamine and add them to 122 g of propylene glycol methyl ether, and heat to 100° C. Add a mixture of 14.4 g of acrylic acid and 15 g of deionized water dropwise, and continue to react for 6 hours after 2 hours of dropwise addition. After the reaction is completed, a liquid product containing acrylic isothiazolinone antifouling monomer is obtained.

[0031] 15 g of propylene glycol methyl ether and 57 g of xylene were added to a 500 mL four-necked flask, heated to 100 °C, and nitrogen was introduced. 5 g of the liquid product containing acrylic isothiazolinone antifouling monomer, 45 g of vinyl polydimethylsiloxane, 15 g of butyl acrylate, and 30 g of 2-ethylhexyl acrylate were mixed to form a mixed monomer, and the mixed monomer was added dropwise to the four-necked flask and dripped within 6 hours; during the dripping process, magnetic stirring was performed at a speed of 600 rpm. After the mixed monomer was dripped, a solution of 1 g of benzoyl peroxide dissolved in 20 g of xylene was dripped, and the dripping was continued for 0.5 hours. The subsequent reaction was completed for 1.5 hours, and the polar antifouling resin was obtained after the reaction was completed.

[0032] Implementation Example 2

[0033] The method is basically the same as Example 1, except that the amounts of the liquid product containing acrylic isothiazolinone antifouling monomer and vinyl polydimethylsiloxane added in the mixed monomer are 15 g and 35 g, respectively.

[0034] Implementation Example 3

[0035] The method is basically the same as Example 1, except that the added amounts of the liquid product containing acrylic isothiazolinone antifouling monomer and vinyl polydimethylsiloxane in the mixed monomer are 25 g and 25 g respectively.

[0036] Implementation Example 4

[0037] The method is basically the same as Example 1, except that the amounts of the liquid product containing acrylic isothiazolinone antifouling monomer and vinyl polydimethylsiloxane added in the mixed monomer are 35 g and 15 g, respectively.

[0038] Implementation Example 5

[0039] The method is basically the same as Example 1, except that the added amounts of the liquid product containing acrylic isothiazolinone antifouling monomer and vinyl polydimethylsiloxane in the mixed monomer are 45 g and 5 g, respectively.

[0040] The polar antifouling resins prepared in Examples 1 to 5 were respectively spin-coated on polished tinplate sheets, and dried at 25°C for 48 hours to form films, thereby preparing test samples. Acrylic silane antifouling resin, acrylic boron antifouling resin, acrylic copper antifouling resin, acrylic zinc silicon antifouling resin, and acrylic zinc antifouling resin were respectively spin-coated on polished tinplate sheets in the same spin-coating manner as the test samples, and dried at 25°C for 48 hours to form films, thereby preparing comparative samples, which were respectively counted as comparative sample 1, comparative sample 2, comparative sample 3, comparative sample 4, and comparative sample 5.

[0041] The impact resistance test was carried out in accordance with GB / T 1732-1993 using a walk-in constant temperature and humidity test chamber; the flexibility test was carried out in accordance with GB / T1731-1993; and the antibacterial and antifouling test was carried out using Gram-positive bacteria Staphylococcus aureus. The test results of the above test samples and comparison samples are shown in Table 1.

[0042]

[0043] From comparative sample 1 to comparative sample 5, none of them has excellent impact resistance, flexibility and good antibacterial property at the same time. The polar antifouling resin synthesized by the present invention has the above excellent properties. The more the amount of acrylic isothiazolinone antifouling monomer added, the better the antibacterial property of the resin; the more the amount of vinyl polydimethylsiloxane added, the better the impact resistance and flexibility of the resin.

Claims

1. A method for preparing a polar ocean antifouling resin, characterized in that: The method comprises the following steps: (1) reacting a chlorine-containing isothiazolinone fungicide with acrylic acid under the catalysis of triethylamine, and obtaining an acrylic isothiazolinone antifouling monomer after the reaction is completed; (2) The polar marine antifouling resin is obtained by randomly or block polymerizing acrylic silane isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate to form acrylic silane isothiazolinone.

2. The method for preparing the polar ocean antifouling resin according to claim 1, characterized in that: The method comprises the following steps: (1) adding a chlorine-containing isothiazolinone fungicide and triethylamine to propylene glycol methyl ether, raising the temperature to 90-100° C., and then dropping a mixture of acrylic acid and deionized water. After the dropping is completed, the reaction is continued until the reaction is complete. After the reaction is completed, a liquid product containing acrylic acid isothiazolinone antifouling monomer is obtained; (2) A liquid product containing acrylic isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate are mixed to form a mixed monomer; propylene glycol methyl ether and xylene are mixed and heated to 90-100° C., and the mixed monomer is added dropwise under nitrogen protection. After the addition is completed, a xylene solution of benzoyl peroxide is added to continue the reaction. After the reaction is completed, a polar marine antifouling resin is obtained.

3. The method for preparing the polar ocean antifouling resin according to claim 2, characterized in that: In the step (1), the mass ratio of acrylic acid to chlorine-containing isothiazolinone fungicide is 1:1-5; the amount of triethylamine used is 0.75-3 times the mass of acrylic acid; the mass ratio of acrylic acid to deionized water is 1:1-3; and the amount of propylene glycol methyl ether used is 6-9 times the mass of acrylic acid.

4. The method for preparing the polar ocean antifouling resin according to claim 2, characterized in that: In the step (2), the mass ratio of the liquid product containing acrylic isothiazolinone antifouling monomer, vinyl polydimethylsiloxane, butyl acrylate and 2-ethylhexyl acrylate is 5-50:5-45:10-25:5-30; the amount of propylene glycol methyl ether is 6-8% of the weight of the mixed monomers, and the amount of xylene is 23-32% of the weight of the mixed monomers; the amount of benzoyl peroxide xylene solution is 0.9-1.6 times the mass of butyl acrylate, and the mass ratio of benzoyl peroxide to xylene in the benzoyl peroxide xylene solution is 1:12-25.

5. The method for preparing the polar ocean antifouling resin according to claim 2, characterized in that: In the step (2), the dropwise addition of the mixed monomers and / or the subsequent reaction after the dropwise addition is carried out under magnetic stirring.

6. The method for preparing the polar ocean antifouling resin according to claim 2, characterized in that: In the step (1), the time for adding the mixture of acrylic acid and deionized water is 1.5-3 hours, and the time for continuing the reaction after the addition is 4-6 hours.

7. The method for preparing the polar ocean antifouling resin according to claim 2, characterized in that: In the step (2), the dropwise addition time of the mixed monomer is 3-10 hours, and the reaction time after the addition of the xylene solution of benzoyl peroxide is 1-4 hours.

8. The method for preparing the polar ocean antifouling resin according to any one of claims 1 to 7, characterized in that: The chlorine-containing isothiazolinone fungicide is 5-chloro-2-methyl-4-isothiazoline-3-one or 4,5-dichloro-N-octyl-4-isothiazoline-3-one.

9. The method for preparing the polar ocean antifouling resin according to any one of claims 1 to 7, characterized in that: The weight average molecular weight of the vinyl polydimethylsiloxane is 1000-5000.

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