阅读说明：本技术 一种油酸接枝丙烯酸锌环氧树脂基涂料及其制备方法 (Oleic acid grafted zinc acrylate epoxy resin-based paint and preparation method thereof ) 是由 谢志鹏 王晶晶 王洪仁 邓喜玲 于 2021-06-21 设计创作，主要内容包括：本发明提供了一种油酸接枝丙烯酸锌环氧树脂基涂料及其制备方法,该涂料由油酸接枝丙烯酸锌聚合物、环氧树脂、松香液、氧化亚铜、氧化锌、辅助防污剂、颜料、触变剂、增塑剂在溶剂介质中,通过分散工艺分散物料,使之混合均匀,且细度达80µm以下,本专利采用长链油酸接枝丙烯酸锌聚合物作为涂层主要成膜剂,提高漆膜柔韧性,消除涂层应力；同时添加少量环氧树脂消除树脂水解后所产生的应力,如树脂/颜填料界面应力和水解后钙化树脂骨架界面应力,避免涂层在淡水环境下因渗透压变化较大,形成开裂等异常现象,保证其具有稳定的耐用性。(The invention provides an oleic acid grafted zinc acrylate epoxy resin-based coating and a preparation method thereof, wherein the coating is prepared by dispersing materials in a solvent medium by an oleic acid grafted zinc acrylate polymer, epoxy resin, rosin liquid, cuprous oxide, zinc oxide, an auxiliary antifouling agent, a pigment, a thixotropic agent and a plasticizer through a dispersion process, so that the materials are uniformly mixed, and the fineness reaches below 80 mu m; meanwhile, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, so that abnormal phenomena of cracking and the like caused by large osmotic pressure change of a coating in a fresh water environment are avoided, and stable durability of the coating is ensured.)

1. An oleic acid grafted zinc acrylate epoxy resin-based paint is characterized in that: the coating comprises the following components in parts by mass: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.

2. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the rosin solution is obtained by dissolving rosin in a solvent xylene, wherein the mass solubility of the rosin is 55-65%, and the rosin is one or a combination of rosin and modified rosin.

3. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.

4. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: cuprous oxide with water content less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.

5. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.

6. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the pigment is permanent red, the thixotropic agent is polyamide wax, and the plasticizer is one or a combination of more of R40 chlorinated paraffin and R70 chlorinated paraffin.

7. The oleic acid grafted zinc acrylate epoxy resin-based coating of claim 1, wherein: the solvent is one or more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate, and isoamyl acetate.

8. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above order, and performing first high-speed dispersion by using a high-speed dispersion machine for 2-4 hours until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 25-35 min until the particle size is smaller than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 5-20 min until the thixotropic agent is uniformly dispersed, filtering and discharging.

9. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 20-30 hours until the particle size is less than or equal to 80 mu m;

and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.

10. The preparation method of the oleic acid grafted zinc acrylate epoxy resin-based paint according to any one of claims 1 to 7, characterized by comprising the following steps: the preparation method comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the sequence, and performing sand grinding dispersion by using a sand mill for 0.8-1.8 hours until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 20-40 min until the particle size is smaller than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.

Technical Field

The invention relates to the technical field of chemical materials, is suitable for ship antifouling coatings, and particularly relates to an oleic acid grafted zinc acrylate epoxy resin-based coating and a preparation method thereof.

Background

At present, shipbuilding factories in mainland areas in China are generally positioned in fresh water river water areas near sea entrances, ships need to be built in the fresh water areas for a long time in an upper-layer building process in the ship building process, and as the osmotic pressure of fresh water is far higher than that of seawater, the antifouling paint often has the adverse phenomena of falling, bubbling and cracking in the fresh water, so that the ships need to be docked and then coated and repaired after the construction is finished, the construction period is influenced, and the construction cost is increased.

Aiming at the problem of special water areas for ship construction in China continental area, relevant researches are carried out by foreign coating huge heads. The self-polishing antifouling paint which adopts acrylic silane polymer as resin base material is developed by the Japan intermediate coat industry, and the water absorption of the coating is reduced by adding hydrophobic alicyclic compound, so that the self-polishing antifouling paint has the applicability of fresh water resistance; the Nippon paint company and Mitsubishi company jointly develop the antifouling paint which takes vinyl resin as a resin base material, and the water absorption of the coating is reduced by utilizing the hydrophobicity of the vinyl resin, so that the fresh water applicability of the antifouling paint is endowed.

Disclosure of Invention

In order to solve the problems, the invention provides the oleic acid grafted zinc acrylate epoxy resin-based paint and the preparation method thereof, the antifouling paint is suitable for a freshwater environment, the problems of easy falling, cracking, foaming and the like caused by freshwater soaking of an antifouling coating are solved, and the long-term freshwater resistance requirement of the antifouling paint is realized.

The technical scheme adopted by the invention for solving the technical problems is as follows: an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following components in parts by weight: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.

Furthermore, rosin is dissolved in a solvent xylene to obtain a rosin solution with mass solubility of 55-65%, and the rosin is one or a combination of more of rosin and modified rosin.

Further, the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.

Furthermore, the cuprous oxide has a water content of less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.

Furthermore, the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.

Further, the pigment is permanent red, the thixotropic agent is polyamide wax, and one or a combination of more of plasticizers R40 chlorinated paraffin and R70 chlorinated paraffin.

Further, the solvent is one or a combination of more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.

A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above order, and performing first high-speed dispersion by using a high-speed dispersion machine for 2-4 hours until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 25-35 min until the particle size is smaller than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 5-20 min until the thixotropic agent is uniformly dispersed, filtering and discharging.

A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 20-30 hours until the particle size is less than or equal to 80 mu m;

and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.

A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the sequence, and performing sand grinding dispersion by using a sand mill for 0.8-1.8 hours until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 20-40 min until the particle size is smaller than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.

The invention has the beneficial effects that: according to the preparation method of the fresh water-resistant self-polishing antifouling paint based on the oleic acid grafted zinc acrylate/epoxy resin matrix, the long-chain oleic acid grafted zinc acrylate polymer is used as a main film forming agent of a coating, so that the flexibility of the paint film is improved, and the stress of the coating is eliminated; meanwhile, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, so that abnormal phenomena of cracking and the like caused by large osmotic pressure change of a coating in a fresh water environment are avoided, and stable durability of the coating is ensured.

Drawings

FIG. 1 is a graph showing the test condition of the antifouling paint of the present invention after being soaked in fresh water for 12 months;

FIG. 2 is a graph showing the antifouling paint of the present invention without seawater alternation between wetting and drying;

FIG. 3 is a graph showing the test results of the antifouling paint of the present invention after seawater wetting and drying alternation for 8 months.

Detailed Description

The embodiments of the present invention are described in detail with reference to the accompanying drawings, and the embodiments and specific operations of the embodiments are provided on the premise of the technical solution of the present invention, but the scope of the present invention is not limited to the following embodiments.

An oleic acid grafted zinc acrylate epoxy resin-based paint comprises the following components in parts by weight: 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 0.5-1 part of thixotropic agent, 2-4 parts of plasticizer and 5-8 parts of solvent.

Furthermore, rosin is dissolved in a solvent xylene to obtain a rosin solution with mass solubility of 55-65%, and the rosin is one or a combination of more of rosin and modified rosin.

Further, the epoxy resin is one or a combination of E51 epoxy resin and E44 epoxy resin.

Furthermore, the cuprous oxide has a water content of less than 0.1%; the zinc oxide has water content and water soluble matter content less than 0.15%.

Furthermore, the auxiliary antifouling agent is one or a combination of several of ECONEA, copper pyrithione, zinc pyrithione and zineb.

Further, the pigment is permanent red, the thixotropic agent is polyamide wax, and one or a combination of more of plasticizers R40 chlorinated paraffin and R70 chlorinated paraffin.

Further, the solvent is one or a combination of more of xylene, n-butanol, ethyl acetate, coal tar, cyclohexanone, acetophenone, isobutanol, isopropanol, methyl acetate and isoamyl acetate.

The molecular formula of the resin base material oleic acid grafted zinc acrylate polymer is as follows:

a preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a high-speed dispersion method and comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above sequence, and performing first high-speed dispersion by using a high-speed dispersion machine for 3 hours until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary high-speed dispersion for 30min until the particle size is less than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 10min until the thixotropic agent is uniformly dispersed, filtering and discharging.

A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a ball milling method and comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 30-40 parts of cuprous oxide, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment, 2-4 parts of plasticizer and 5-8 parts of solvent, adding the materials into a dispersion tank according to the sequence, and performing ball milling for 24 hours until the particle size is less than or equal to 80 mu m;

and step two, adding 0.5-1 part of thixotropic agent into a dispersion tank, continuously performing ball milling until the thixotropic agent is uniformly dispersed, filtering and discharging.

A preparation method of an oleic acid grafted zinc acrylate epoxy resin-based paint adopts a sanding dispersion method, and comprises the following preparation steps:

weighing 15-20 parts of oleic acid grafted zinc acrylate polymer, 1-3 parts of epoxy resin, 10-20 parts of rosin liquid, 7-10 parts of zinc oxide, 3-7 parts of auxiliary antifouling agent, 0.5-1 part of pigment and 2-4 parts of plasticizer according to the mass parts, adding the materials into a dispersion tank in the above sequence, and performing sand grinding dispersion by using a basket type sand mill or a horizontal sand mill for 1h until the particle size is less than or equal to 80 mu m;

continuously adding 30-40 parts of cuprous oxide and 5-8 parts of solvent into a dispersion tank, and performing secondary sanding dispersion for 30min until the particle size is smaller than or equal to 80 mu m;

and step three, adding 0.5-1 part of thixotropic agent into the dispersion tank, continuously dispersing for 20-40 min until the thixotropic agent is uniformly dispersed, filtering and discharging.

The invention discloses a preparation method of a freshwater-resistant self-polishing antifouling coating based on oleic acid grafted zinc acrylate/epoxy resin, which adopts a long-chain oleic acid grafted zinc acrylate polymer as a main film-forming agent of a coating, improves the flexibility of the coating and eliminates the stress of the coating; simultaneously, a small amount of epoxy resin is added to eliminate stress generated after resin hydrolysis, and the action schematic diagram of the epoxy resin for reducing the stress of the coating is as follows:

such as resin/pigment filler interface stress and calcified resin skeleton interface stress after hydrolysis, avoids abnormal phenomena of cracking and the like of the coating due to large osmotic pressure change in a fresh water environment, and ensures that the coating has stable durability.

Example 1

The ingredients of this example are shown in table 1, and the coating is prepared by a ball milling method in this example;

example 2

The ingredients of this example are shown in table 1, and the coating is prepared by a high-speed dispersion method in this example;

example 3

The ingredients of this example are shown in table 1, and the coating is prepared by a sand milling method;

the addition amounts of the substances in the examples in Table 1 are parts by mass;

table 1 formulation of the coatings of the different examples

1) The surface change of the paint prepared by the invention is shown in figure 1 when the paint is coated on a sample plate and soaked in fresh water for 12 months, and as can be seen from figure 1, the antifouling paint prepared by the invention does not have obvious phenomena of shedding, cracking and foaming on the surface after being soaked in fresh water for 12 months, which shows that the antifouling paint prepared by the invention has good fresh water soaking resistance.

2) The coating prepared by the invention is coated on a sample plate, and is soaked in seawater for 8 months of seawater wet-dry alternation, the sample figure before soaking is shown in figure 2, the surface change situation is shown in figure 3, and figure 3 shows that the antifouling coating prepared by the invention has no obvious phenomena of shedding, cracking and foaming on the surface after 8 months of seawater wet-dry alternation, which indicates that the antifouling coating prepared by the invention has good seawater wet-dry alternation resistance.

The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.