CN1709921A - Zinc or copper acrylate resin containing indole functional group and its preparation method and application - Google Patents

Abstract

This is a kind of acrylic zinc or cuprum resin containing indole functional group and its preparation method. Its characteristics are: firstly prepare monomer containing indole functional group, then synthesize acrylic resin containing functional group and carboxyl, finally make the acrylic resin and zinc hydroxide or cuprum hydroxide react to obtain acrylic zinc or cuprum resin containing indole functional group; the reaction temperature of the said synthesizing monomer containing indole functional group is -10 - 10 Deg. C, the reaction time is 1.5 - 5 hours. The resin of the invention can be used for preparing sea antifouling dope. In the seawater, the organic zinc or cuprum acrylic ester on the polymer linear main chain of the coat surface hydrolyzes, and send out organic zinc or cuprum; the hydrolyzed polymer main chain contains indole functional group with highly efficient antifouling activeness, which makes the hydrolyzed polymer main chain still has sterilization activeness. So the dope can effectively prevent halobios from clinging on the surface of fishing tools, ships and seacoast establishments, and has good antifouling performance.

Description

Zinc or copper acrylate resin containing indole functional group and its preparation method and application

technical field

The invention relates to a zinc or copper acrylate resin, in particular to a zinc or copper acrylate resin containing an indole functional group, a preparation method thereof and an application in preparation of marine antifouling paint.

technical background:

There are thousands of fouling organisms in the ocean, and more than half of these fouling organisms float on the coast and harbors. They attach and grow on the bottom of ships, buoys, water pipelines, cooling pipelines, rafts and nets. The attachment of these fouling organisms will cause the surface fouling of these facilities, increase the surface friction resistance, and also accelerate the corrosion rate. The most common solution to marine biofouling is to apply paints containing antifouling agents. At present, a large number of antifouling coatings used at home and abroad contain organotin and cuprous oxide, for example, a copolymer of tributyltin methacrylate and methyl methacrylate and cuprous oxide (Cu ₂ O) is used as a composition Anti-fouling coatings, coated on the bottom of ships and other surfaces, can effectively prevent the harm of marine fouling organisms. Harmful attachments (barnacles, sea squirts, seaweed, etc.) on the surface of the facility have a killing effect. But at the same time, TBT can cause sex variation and shell distortion of oysters, cockles and mussels, seriously endangering the marine ecological environment and marine aquaculture. The most famous TBT-containing self-polishing antifouling coating is European Patent No. EP-A-51930. This patent is a milestone in the disclosure of TBT copolymers. Since then, TBT antifouling coatings have dominated the market for 20 years. It was not until 1987 that people realized that this organotin compound was highly toxic, would pollute the environment, and even affect human health through the food chain. For this reason, there is a need to develop tin-free marine antifouling coatings to replace organotin marine antifouling coatings.

Invention content:

The purpose of the present invention is to provide a kind of zinc or copper acrylate resin containing indole functional group and preparation method thereof, and apply it to the preparation of marine antifouling coatings, to make up for the above-mentioned needs of the prior art.

A zinc acrylate or copper resin containing an indole functional group is characterized in that the structural formula is:

In the formula, R is an acid radical of an organic acid, the organic acid is benzoic acid, m-toluic acid, p-toluic acid or naphthenic acid, R ₁ is H or CH ₂ N(CH ₃ ) ₂ , X is H or CH ₃ , _X1 is H, Cl or Br, _X2 is H, Cl or Br, and B is the rest of the ethylenically unsaturated monomer.

The preparation method of above-mentioned acrylate zinc or copper resin containing indole functional group is characterized in that firstly prepare the monomer containing indole functional group, then synthesize the acrylic resin containing indole functional group and carboxyl group at the same time, finally make the acrylic resin and zinc hydroxide or copper hydroxide reaction to obtain zinc acrylate or copper resin containing indole functional groups; the reaction temperature of the described synthesis containing indole functional group monomers is -10～10°C, and the reaction time is 1.5～5 hours. Simultaneously, the reaction temperature of the acrylic resin containing indole functional group and carboxyl group is 75-150°C, and the reaction time is 0.5-4 hours. , The reaction time is 3～12 hours.

Application of the zinc or copper acrylate resin containing indole functional groups in the preparation of marine antifouling coatings.

The resin of the present invention can be used to prepare marine antifouling coatings. In seawater, the organic zinc or copper acrylate on the polymer linear main chain on the coating surface is hydrolyzed to release organic zinc or copper, and the polymer main chain after hydrolysis The chain also contains indole functional groups with high antifouling activity, so that the polymer chain after hydrolysis still has bactericidal activity, so the coating can effectively prevent marine organisms from attaching to the surface of nets, ships and coastal facilities, etc. Good dirt performance.

Detailed ways

1. Preparation of 1-acryloyl indole monomer

Put 50mL of freshly steamed tetrahydrofuran, 3.5g of 1-hydroindole, and 3.9g of sodium cyanide in a three-necked flask in sequence, and react at room temperature for 30 minutes to obtain indole sodium salt. Dissolve 3.3 g of acryloyl chloride in 10 mL of tetrahydrofuran, drop it into the indole sodium salt prepared above, control the reaction temperature at 0° C., and react for 2.5 hours to obtain 1-acryloyl indole monomer.

Replace the above-mentioned 1-hydroindole with haloindole, 1-hydrohydrophylline or halocarpine, and follow the above-mentioned preparation method to obtain 1-acryloyl haloindole, 1-acryloyl Alkaline or 1-acryloylhalocarpine monomer.

2. Preparation of acrylic resin containing indole functional groups and carboxyl groups

In a three-necked flask equipped with a stirring device, a condenser, and a thermometer, add toluene and n-butanol 262g of a mixed solvent whose weight ratio is 4:1, raise the temperature to about 105°C, and then dropwise add 30g of 1- A mixed solution of acryloyl indole, 30g of acrylic acid, 47g of methyl methacrylate, 64g of ethyl acrylate, 29g of butyl acrylate, and 4g of azobisisobutyronitrile (AIBN), reacted for two hours and then added within half an hour Containing 2g of initiator AIBN, 30g of mixed solvent of toluene and n-butanol in a weight ratio of 4:1, the reaction was completed after incubation for 1.5 hours.

If the above-mentioned 1-acryloyl indole is replaced with 1-acryloyl haloindole, 1-acryloyl halophylline or 1-acryloyl halophylline, the corresponding acryloyl derivatives on the molecular chain can also be obtained. The weight percentage of the corresponding acryloyl derivative group in the polymer is 2-50%.

The ethylenically unsaturated monomers described in the present invention are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate ester, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, styrene, vinyl acetate, vinyl butyrate or vinyl chloride; the organic solvent is toluene, n-butanol, xylene , ethyl acetate, butyl acetate, dimethylformamide, cyclohexanone or methyl isobutyl ketone; the free radical initiator is azobisisobutyronitrile or benzoyl peroxide; the acrylic acid The weight percentage in the copolymer is 2-26%.

3. Preparation of zinc indole acrylate resin

Benzoic acid 30.6g, Zn(OH) ₂ 24g, above-mentioned acrylic resin 300g containing indole functional group and carboxyl group, butyl acetate 114g, the mixed solvent 60g of toluene and n-butanol that the weight ratio is 4:1 are added simultaneously In a three-necked flask with a stirring device, a condenser, an oil-water separator, and a thermometer. Keep the reaction temperature at 80°C. After 7 hours, the reaction mixture tends to a transparent state, and the temperature is raised to 125°C for dehydration. After making sure that no water is distilled off, the reaction is terminated to obtain a zinc or copper acrylate resin containing indole functional groups.

Resins of zinc or copper acrylate containing indole functional groups can also be obtained by replacing the above-mentioned benzoic acid with m-toluic acid, p-toluic acid or naphthenic acid.

Resin of the present invention can be used for preparing marine antifouling paint, and this marine antifouling paint is made up of resin solution of the present invention, plasticizer, one or more fillers and one or more antifouling agents, and their weight percent range They are 20-60, 1-20, 1-30 and 1-50 respectively. During preparation, the ethyl acetate solution of 50g indole zinc acrylate resin of the present invention, 2.5g chlorinated paraffin, 12g iron oxide red, 2.5g fumed silica, 33g 4,5 - The mixture of dichloro-2-butoxypropyl-4-isothiazolin-3-one was shaken for 2 hours in a paint shaker containing glass beads, then filtered through a 100-mesh filter. In order to test the antifouling performance of the obtained antifouling paint, refer to the national standard "Shoal Sea Immersion Test Method for Antifouling Paint Sample" (GB5370-85), and paint the antifouling paint on a plate with a length of 250 mm, a width of 150 mm, and a thickness of On the 2mm low-carbon steel test model, the test model is fixed with iron bolts at both ends of a rectangular wooden strip with grooves. The experimental model was hung in the deep-sea cage culture area (2 years) of Xunshan Town, Rongcheng City, and quite good experimental results were obtained, as shown in the table below. 6 months 12 months 24 months blank template 20 40 100 Sample soaked in antifouling paint 0 0 3

Note: 0, 3, 20, 40, and 100 are the percentages of the attachment area of marine organisms on the sample plate.

When preparing marine antifouling coatings, the above-mentioned zinc indole acrylate resin can also be used instead of zinc indole acrylate or copper resin of the present invention, zinc catarrhine acrylate or copper resin or zinc acrylate halide or copper resin The organic solvent ethyl acetate used can be replaced by butyl acetate, xylene, toluene or butanol; the plasticizer vaseline used can be replaced by chlorinated paraffin, dibutyl phthalate or dioctyl phthalate Esters; the red iron oxide filler used can be replaced by talcum powder, titanium dioxide, fumed silica or zinc oxide, all of which can obtain obvious results.

Claims (7)

1, a kind of resin containing zinc acrylate or copper of indole functional group, it is characterized in that structural formula is: In the formula, R is an acid radical of an organic acid, the organic acid is benzoic acid, m-toluic acid, p-toluic acid or naphthenic acid, R ₁ is H or CH ₂ N(CH ₃ ) ₂ , X is H or CH ₃ , _X1 is H, Cl or Br, _X2 is H, Cl or Br, and B is the rest of the ethylenically unsaturated monomer. 2, the preparation method of the zinc acrylate or copper resin containing indole functional group described in claim 1, it is characterized in that first prepare the monomer containing indole functional group, then synthesize the acrylic resin containing indole functional group and carboxyl group simultaneously, finally use The acrylic resin reacts with zinc hydroxide or copper hydroxide to obtain zinc or copper acrylate resin containing indole functional groups; the reaction temperature of the synthesis of monomers containing indole functional groups is -10～10°C, and the reaction time is 1.5～ 5 hours, the reaction temperature of the acrylic resin containing indole functional groups and carboxyl functional groups is 75-150°C, and the reaction time is 0.5-4 hours. The synthesis of zinc or copper acrylate resins containing indole functional groups The reaction temperature is 80-150°C, and the reaction time is 3-12 hours. 3. The preparation method as claimed in claim 2, characterized in that the preparation of the monomer containing indole functional group is to make acryloyl chloride and 1-hydroindole, 1-hydrohalogenated indole, 1-hydroreed Alkaline or 1-hydrohalophylline reaction; the monomer containing indole functional group is 1-acryloyl indole, 1-acryloyl haloindole, 1-acryloyl agrophylline or 1-propylene Acyl halide agrophylline. 4. The preparation method according to claim 2, characterized in that the indole functional group monomers in the acrylic resin containing indole functional groups and carboxyl groups are 1-acryloyl indole, 1-acryloyl halide indole 1. One or more of 1-acryloyl agrophylline and 1-acryloyl halide agrophylline, the content of which in the copolymer is 2-50% by weight. 5. The preparation method according to claim 2, characterized in that the ethylenically unsaturated monomers in the acrylic resin containing indole functional groups and carboxyl groups are methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, tert-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, styrene, Vinyl acetate, vinyl butyrate or vinyl chloride; The organic solvent is toluene, n-butanol, xylene, ethyl acetate, butyl acetate, dimethylformamide, cyclohexanone or methyl isobutyl ketone One or several kinds; the free radical initiator is azobisisobutyronitrile or benzoyl peroxide; the weight content of the acrylic acid in the copolymer is 2-26%. 6. The application of the indole functional group-containing zinc or copper acrylate resin according to claim 1 in the preparation of marine antifouling coatings. 7. The application as claimed in claim 6, characterized in that the marine antifouling paint consists of the resin solution according to claim 1, plasticizer, one or more fillers and one or more antifouling agent, and their weight percent ranges are 20-60, 1-20, 1-30 and 1-50 respectively; the solvent of the resin solution is ethyl acetate, butyl acetate, xylene, toluene or butanol , the concentration of the resin solution is 20% to 60%.