CN110922828A - Graphene marine antifouling paint and preparation method thereof - Google Patents

Abstract

The invention provides a graphene marine antifouling paint and a preparation method thereof, and belongs to the technical field of paints. The graphene marine antifouling paint solves the problems that the existing marine antifouling paint is poor in seawater impact resistance, easy to adhere marine organisms, low in adhesive force of a paint film after long-time use and the like, and comprises the following components in percentage by weight: 6 to 15 percent of mixed solvent, 20 to 40 percent of resin, 0 to 15 percent of rosin-xylene solution, 0.5 to 5 percent of auxiliary agent, 0.1 to 1 percent of anti-settling agent, 0.1 to 5 percent of graphene, 20 to 35 percent of anti-fouling agent, 5 to 15 percent of filler, 0.1 to 5 percent of pigment and 0.1 to 1.5 percent of coupling agent. The invention has the advantages of good mechanical property, durable antifouling effect, difficult marine organism adhesion and the like.

Description

Graphene marine antifouling paint and preparation method thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a graphene marine antifouling paint and a preparation method thereof.

Background

When a ship sails in the ocean, marine organisms such as bacteria, diatoms, barnacles, oysters, mussels, coiled pipe worms and the like can be attached to the bottom of the ship in a large amount. The attachment of these marine organisms increases the weight of the ship body, increases the roughness of the ship bottom, increases the sailing resistance, finally increases the sailing oil consumption of the ship, and increases the sailing cost. In addition, the secretion of the attached organisms has certain corrosiveness, and damages can be caused to the surfaces of the metal ship shell and the ship bottom, so that the maintenance frequency of the ship is increased, the maintenance cost of the ship is increased, or the service life of the ship is shortened. And a lot of facilities and equipment at the bottom of the ship, such as propellers, water inlets and outlets, stabilizer fins and other structural components, are easily affected by the organisms, and finally the sailing safety is affected.

The antifouling paint is prepared from self-polishing resin and can prevent marine adhesion organisms from adhering to the antifouling paint within a certain period of time. The paint film has a certain water permeability to ensure that the antifouling agent in the paint film steadily and gradually seeps into the seawater, and the paint film maintains slow self-polishing. The adhesion of marine organisms at the bottom of the ship is prevented, and the surface of the bottom of the ship is kept smooth and complete, so that the navigation oil consumption is reduced, and the maintenance cost of the bottom of the ship is reduced.

The marine antifouling paint popular in the market has poor seawater impact resistance under the action of seawater and sunlight, and generates stress concentration after long-time use, so that the adhesion of a paint film is reduced, and mechanical defects such as cracks or falling are generated. Some may even exhibit blistering.

Disclosure of Invention

A first object of the present invention is to solve the above problems in the prior art, and to provide a graphene marine antifouling paint; the second purpose of the invention is to provide a preparation method of the graphene marine antifouling paint.

The first object of the present invention can be achieved by the following technical solutions: the graphene marine antifouling paint is characterized by comprising the following components in percentage by weight: 6 to 15 percent of mixed solvent, 20 to 40 percent of resin, 0 to 15 percent of rosin-xylene solution, 0.5 to 5 percent of auxiliary agent, 0.1 to 1 percent of anti-settling agent, 0.1 to 5 percent of graphene, 20 to 35 percent of anti-fouling agent, 5 to 15 percent of filler, 0.1 to 5 percent of pigment and 0.1 to 1.5 percent of coupling agent.

Preferably, in the mixed solvent, the components comprise, by weight, 30% of xylene, 20% of toluene, 20% of n-butyl acetate, 29% of propylene glycol monomethyl ether acetate and 1% of a dehydrating agent.

Preferably, the resin is an acrylic resin derivative.

Preferably, the resin is selected from one or two of main chain degradation type polyacrylic acid silicon self-polishing resin and hyperbranched zinc self-polishing resin.

Preferably, in the rosin-xylene solution, the mass fraction of rosin is 78%, and the mass fraction of xylene is 22%.

Preferably, the auxiliary agent comprises a dispersing agent, a defoaming agent and a leveling agent, wherein the dispersing agent is a block copolymer containing pigment affinity groups; the defoaming agent is a modified polysiloxane solution; the flatting agent is polyester modified polydimethylsiloxane solution.

Preferably, the dispersant is selected from ELEMENTIS Disponer 9850, ELEMENTIS NUOSPERSE FX9360 or LB S3000 in one or any combination; the defoaming agent is selected from one or two of BYK-066N or ELEMENTIS Defom 6500; the leveling agent is BYK-310.

Preferably, the anti-settling agent is selected from one or any combination of bentonite organic derivatives, polyamide wax, fumed silica and magnesium aluminosilicate.

Preferably, the anti-settling agent is BENTONE SD-2.

Preferably, the graphene is a two-dimensional carbon nanomaterial.

Preferably, the antifouling agent is a mixture of cuprous oxide and an algae inhibitor, and the mass ratio of the cuprous oxide to the algae inhibitor is 30: 1.

preferably, the algistat is selected from one or two of DT-250 and ZPT.

Preferably, the coupling agent is selected from one or any combination of a silane coupling agent, a titanate coupling agent and a zirconium coupling agent.

Preferably, the coupling agent is a silane coupling agent Coatosil MP 200.

The second object of the present invention can be achieved by the following technical solutions: the preparation method of the graphene marine antifouling paint is characterized by comprising the following steps of,

s01, adding the mixed solvent, the resin, the auxiliary agent and the anti-settling agent into a stirring tank according to the proportion, and stirring at the speed of 800r/min for 10min-15 min;

s02, adding graphene, an antifouling agent, a filler and a pigment into the stirring tank in the S01, and dispersing for 15-20 min at the speed of 1000 r/min;

s03, circularly sanding the material in the S02 until the fineness is less than or equal to 20 um;

s04, adding a coupling agent into the material of S03, and stirring at the speed of 600r/min to obtain the graphene marine antifouling paint;

in step S01, a rosin xylene solution may also be added.

The working principle of the invention is as follows:

compared with the prior art, the invention has the following advantages:

1. the graphene marine antifouling paint prepared by the invention has the characteristics of good mechanical property, lasting antifouling effect and convenience in construction, and can effectively avoid the defects of cracking, falling, foaming and the like after a paint film is used for a long time. The method can be widely applied to antifouling and protection of the bottom of a ship and the underwater part of an ocean platform. The construction can be carried out by high-pressure airless spraying, brushing, roller coating and the like.

2. The invention can be used for a long time, the bottom of the ship is not attached by marine organisms, and the power of the ship body is improved.

3. The paint of the invention does not contain organic tin and dichlorodiphenyl trichloroethane, does not cause pollution to the environment and is very environment-friendly.

Detailed Description

The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

The materials were prepared for implementation according to the component formulations of table 1.

Table 1: five example component formulations

Name of raw materials	Example 1	Examples of the invention	Example 3	Example 4	Example 5
						Mixed solvent	7.1	7.1	8.2	11.0	11.0
Main chain degradation type polyacrylic acid silicon self-polishing resin	30.0	0.0	30.0	39.0	/
						Hyperbranched zinc self-polishing resin	/	30.0	/	/	39.0
Rosin-xylene solution	15.0	15.0	15.0	/	/
						Auxiliary agent	5.0	5.0	4.0	4.0	4.0
Anti-settling agent	0.5	0.5	0.4	0.6	0.6
						Graphene	3.0	3.0	2.5	0.5	0.5
Antifouling agent	30.0	30.0	30.0	30.0	30.0
						Filler material	7.5	7.5	8.0	13.0	13.0
Pigment (I)	1.5	1.5	1.5	1.5	1.5
						Coupling agent	0.4	0.4	0.4	0.4	0.4
Total up to	100	100	100	100	100

The mixed solvent used in the examples is self-made. The composition comprises the following components in percentage by weight: 30% of dimethylbenzene, 20% of methylbenzene, 20% of n-butyl acetate, 29% of propylene glycol monomethyl ether acetate and 1% of BF-5 dehydrating agent. Adding the above solvents into a stirrer in proportion, uniformly stirring, and packaging for later use.

The resins used in the examples are acrylic resin derivatives. Comprises one or two of main chain degradation type polyacrylic acid silicon self-polishing resin and hyperbranched zinc self-polishing resin. The main chain degradation type polyacrylic acid silicon self-polishing resin is main chain degradation type polyacrylic acid silane ester self-polishing resin, and the main chain polyester can be broken through degradation while the hydrolysis characteristic of side chain silane ester is kept, so that the hydrolysis property of the silicon alkyl ester in the self-polishing resin and the solubility of the polymer are effectively coordinated. In seawater, it can degrade at a constant rate, continuously self-renew its surface, and realize the controlled release of antifouling agent.

The rosin-xylene solutions in the examples were all in a mass ratio of 72: 28, and (3) preparing. Wherein the rosin accounts for 72 percent and the dimethylbenzene accounts for 28 percent. Adding the rosin into dimethylbenzene, placing the mixture in a 120 ℃ oven for 1 hour, taking out the mixture after the rosin is completely dissolved, and uniformly stirring the mixture for later use.

The auxiliaries in the examples are dispersants, defoamers and leveling agents. The proportion is 25: 5: 3. the dispersing agent, the defoaming agent and the flatting agent are common auxiliary agents suitable for oily systems on the market.

The anti-settling agent in the embodiment is bentonite Bentonie SD-2.

The graphene in the embodiment is graphene developed and produced by Hangzhou alkene science and technology limited. The graphene is produced by a physical stripping method and has a complete crystal structure. The paint can effectively improve the mechanical property and the adhesive force of a paint film and prolong the service life of the paint film when added into the paint. In addition, the graphene is a hydrophobic substance, so that the resistance between the ship body and water can be reduced after the graphene is added, the navigational speed is improved, and fuel is saved. The sheet diameter of the graphene is 21-25 mu m, the layer number is 11-15, the purity of the graphene is more than 95 wt%, the thickness is 1 nm-20 nm, the transverse dimension of a plane is in a range of 1 um-100 um, and the physical stripping method is one of a micro-mechanical stripping method and a liquid-phase or gas-phase direct stripping method.

The antifouling agent in the embodiment is a mixture of cuprous oxide and an algae inhibitor, and the mass ratio of the antifouling agent is 30: 1. the algistat is a compound algistat, and is one or two of DT-250 and ZPT of Jianbang chemistry. The used algistat is environment-friendly and pollution-free. Has obvious antifouling effect on marine fouling organisms. The preparation proportion of the cuprous oxide and the algistat can be adjusted according to different requirements, and the change of the preparation proportion has certain decisive influence on prolonging the service life of the antifouling paint.

The filler in the examples was 1250 mesh technical grade talc.

The pigments in the embodiment are randomly selected according to the colors required by the ship body or the underwater part of the ocean platform in practical application, or are red, or are gray, or are other single colors, or are composite colors.

The coupling agent in the examples is a Coatosil MP200 silane coupling agent.

Example 1: the preparation process comprises the following steps:

(1) adding the mixed solvent, the resin, the rosin xylene solution, the auxiliary agent and the anti-settling agent into a stirring tank according to the weight ratio of the formula, then stirring for 10min-15min in a high-speed dispersion machine at the speed of 800r/min, and uniformly stirring.

(2) Slowly adding graphene, an antifouling agent, a filler and a pigment into the stirring tank in the step (1), dispersing at a high speed of 1000r/min for 15min-20min, and uniformly stirring for later use.

(3) And (3) pumping the material in the step (2) to a horizontal sand mill for circular sanding until the fineness is less than or equal to 20 um.

(4) Transferring the material in the step (3) to a paint mixing cylinder, adding a coupling agent, and uniformly stirring at the speed of 600 r/min.

(5) And (5) detecting the stirred materials in the step (4), filtering, weighing and packaging after the materials are qualified to obtain the graphene ship antifouling paint.

The preparation steps of example 2, example 3, example 4 and example 5 refer to example 1. The invention will be explained in more detail by means of five embodiments, which are not limited to the 5 examples given, but are intended to protect all variations and modifications within the scope of the invention.

The performance of the graphene ship antifouling paint is detected according to the national relevant standard GBT 6822-2014 ship antifouling and antirust paint system, and the test results are shown in Table 2.

Table 2 shows the performance results of the graphene marine antifouling paint.

The detection result shows that the graphene ship antifouling paint has good antifouling performance, mechanical property and construction performance, and is suitable for coating and protecting underwater parts of ships and ocean platforms.

The invention has been applied to Hainan Sandliage and sand carriers. After the ship is used for half a year, no marine organism is attached to the bottom of the ship, the power of the ship is improved, and the ship is approved by users.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (10)

1. The graphene marine antifouling paint is characterized by comprising the following components in percentage by weight: 6 to 15 percent of mixed solvent, 20 to 40 percent of resin, 0 to 15 percent of rosin-xylene solution, 0.5 to 5 percent of auxiliary agent, 0.1 to 1 percent of anti-settling agent, 0.1 to 5 percent of graphene, 20 to 35 percent of anti-fouling agent, 5 to 15 percent of filler, 0.1 to 5 percent of pigment and 0.1 to 1.5 percent of coupling agent.

2. The graphene marine antifouling paint as claimed in claim 1, wherein the mixed solvent comprises 30% by weight of xylene, 20% by weight of toluene, 20% by weight of n-butyl acetate, 29% by weight of propylene glycol methyl ether acetate, and 1% by weight of a dehydrating agent.

3. The graphene marine antifouling paint according to claim 1, wherein the resin is selected from one or a combination of two of backbone-degradable polyacrylic acid silicon self-polishing resin and hyperbranched zinc self-polishing resin.

4. The graphene marine antifouling paint according to claim 1, wherein the rosin-xylene solution contains 78% by mass of rosin and 22% by mass of xylene.

5. The graphene marine antifouling paint according to claim 1, wherein the auxiliary agent comprises a dispersant, a defoamer and a leveling agent, and the dispersant is a block copolymer containing pigment affinity groups; the defoaming agent is a modified polysiloxane solution; the flatting agent is polyester modified polydimethylsiloxane solution.

6. The graphene marine antifouling paint according to claim 1, wherein the anti-settling agent is selected from one or any combination of bentonite organic derivatives, polyamide wax, fumed silica and magnesium aluminosilicate.

7. The graphene marine antifouling paint according to claim 1, wherein the graphene is a two-dimensional carbon nanomaterial.

8. The graphene marine antifouling paint as claimed in claim 1, wherein the antifouling agent is a mixture of cuprous oxide and an algae inhibitor, and the mass ratio of the cuprous oxide to the algae inhibitor is 30: 1.

9. the graphene marine antifouling paint according to claim 1, wherein the coupling agent is selected from one or any combination of silane coupling agent, titanate coupling agent and zirconium coupling agent.

10. A method for preparing the graphene marine antifouling paint according to any one of claims 1 to 9,

s01, adding the mixed solvent, the resin, the auxiliary agent and the anti-settling agent into a stirring tank according to the proportion, and stirring at the speed of 800r/min for 10min-15 min;

s02, adding graphene, an antifouling agent, a filler and a pigment into the stirring tank in the S01, and dispersing for 15-20 min at the speed of 1000 r/min;

s03, circularly sanding the material in the S02 until the fineness is less than or equal to 20 um;

s04, adding a coupling agent into the material of S03, and stirring at the speed of 600r/min to obtain the graphene marine antifouling paint;

in step S01, a rosin xylene solution may also be added.