CN119242121A - A fouling-releasing marine antifouling coating with a soft-hard segment coordinated topological structure and a preparation method thereof - Google Patents

Abstract

The invention discloses a fouling release type marine antifouling paint with a soft and hard segment synergistic topological structure, which uses an anionic monomer and a hydrophilic amide monomer as a hard segment structure, uses carboxyl polysiloxane as a soft segment structure, prepares a modified siloxane polymer with a soft and hard segment synergistic molecular structure through an in-situ ester crosslinking reaction, and can effectively improve the entropy of the topological structure of the polymer based on the soft and hard segment synergy, thereby realizing the coordination between the cohesive force and the adhesive force of the polymer and realizing the excellent bonding effect of the modified polymer. In the subsequent preparation of the coating, the hydrophobic siloxane exhibits hydrophobicity and low surface energy characteristics, thereby ensuring that the coating has excellent antifouling properties, while the excellent adhesion effect ensures that the cured coating can be firmly adhered to the substrate or intermediate paint surface. The coating can be applied to marine facility antifouling, and is particularly suitable for various marine facilities immersed in a seawater environment for a long time.

Description

Fouling release type marine antifouling paint with soft and hard segment cooperative topological structure and preparation method thereof

Technical Field

The invention belongs to the technical field of marine antifouling paint and underwater paint protection, and relates to an fouling release type marine antifouling paint with a soft and hard segment synergistic topological structure and a preparation method thereof.

Background

Marine biofouling is a major problem facing the world's developing marine industry, and painting an antifouling paint is the most effective and convenient method to solve this problem.

The organic silicon environment-friendly marine antifouling paint belongs to fouling release type marine antifouling paint, and the adhesion of fouling organisms on the surface of the paint is effectively inhibited by virtue of low surface energy and unique nonpolar of the organic silicon film-forming paint. And the organosilicon coating has lower elastic modulus, and the adhesion organisms can be separated from the surface of the coating in a stripping mode with low energy consumption. For a ship sailing in the ocean, fouling organisms which are not firmly adhered can be easily removed by virtue of water flow scouring action caused by relative motion with seawater. The related coating has great development and application prospect. However, it is also due to the low surface energy properties of silicone resins that cured silicone coatings tend to be difficult to adhere to polar metal substrates. The low adhesion to the metal substrate or the corresponding intermediate coating can lead to large-area stripping and falling off of the corresponding coating during use, especially during long-term service in (sea) water. The problem of easy falling caused by low cohesive force severely limits the wide range of applications of the related organosilicon marine antifouling paint.

Disclosure of Invention

The invention aims to provide the fouling release type marine antifouling paint with the soft and hard segment cooperative topological structure and the preparation method thereof, aiming at the defects that polysiloxane fouling release type marine antifouling paint has poor adhesion with a base material and is easy to fall off and the like.

The technical scheme is that the fouling release type marine antifouling paint with the soft and hard segment cooperative topological structure comprises the following components in parts by weight:

The soft and hard segment synergistic modified polysiloxane polymer has a structure that main chain is hydrophobic methyl siloxane, and both ends are hard segment molecular chain segments from anionic monomers and hydrophilic amide monomers.

Further, the soft and hard segment synergistically modified polysiloxane polymer is prepared by the steps of:

(1) Sequentially adding an anionic monomer, a hydrophilic amide monomer, carboxyl polysiloxane and a second solvent into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the PH to be more than 10 by a mixed solution of sodium hydroxide (1 g)/ethanol (10 g), and stirring and reacting for 10-20 hours at 20-100 rpm under the condition of 40-50 ℃;

(2) Filtering the precipitate after the reaction, washing at least 3 times by using deionized water, and then drying in a vacuum device for 24 hours to obtain the soft and hard segment synergistic modified polysiloxane polymer.

Further, the weight ratio of the anionic monomer to the hydrophilic amide monomer to the carboxyl polysiloxane to the solvent is (3-8)/(5-10)/(50-80)/(100-150).

Further, the anionic monomer is selected from one of sodium 2-carboxyethyl acrylate, sodium indoleacrylate and sodium alginate.

Further, the hydrophilic amide monomer is selected from one of N- (2-hydroxyethyl) acrylamide, methacrylamide and dimethylaminopropyl acrylamide.

Further, the carboxyl polysiloxane is selected from dicarboxyl-terminated polysiloxanes, and the viscosity of the dicarboxyl-terminated polysiloxanes is 2000-5000 mPas at room temperature.

Further, the second solvent is selected from one of ethanol, acetone and toluene.

Further, the auxiliary agent is at least one selected from wetting dispersant, defoamer and leveling agent.

Specifically, the wetting dispersant is selected from one of BYK116, BYK169, and courtesy 901 and 903 of the bikes company.

Specifically, the defoamer is selected from one of BYK065, BYK066N and EFKA2020 of Netherlands Epiff card.

Specifically, the leveling agent is selected from one of Pick BYK308, BYK310 and BYK373 in Germany.

Further, the pigment and filler is selected from one of, but not limited to, calcium carbonate, ferric oxide, titanium dioxide, barium sulfate, kaolin, and zinc oxide.

Further, the first solvent is selected from one of methanol, xylene and acetone.

In the reaction equipment which is protected by nitrogen and is connected with a stirring reflux device in parallel, sequentially adding an anionic monomer, a hydrophilic amide monomer, carboxyl polysiloxane and a second solvent, then adjusting the PH to be more than 10 through a sodium hydroxide/ethanol mixed solution, and stirring and reacting for 10-20 hours at 20-100 rpm under the condition of 40-50 ℃;

(2) Filtering the precipitate after reaction, washing at least 3 times by using deionized water, and then drying in a vacuum device to obtain the soft and hard segment synergistic modified polysiloxane polymer;

(3) Sequentially adding the soft and hard segment synergistic modified polysiloxane polymer and the auxiliary agent obtained in the step 2 into dispersing stirring equipment, adding pigment filler and first solvent into the dispersing stirring equipment after stirring and dispersing, continuously stirring and dispersing to obtain the fouling release type marine antifouling paint with the soft and hard segment synergistic topological structure, and then sealing and storing.

Further, the invention provides a method for preparing the coating by using the coating, the coating is coated by spraying, rolling or brushing, and the coating with the thickness of 150-250 um is prepared by curing for at least 48 hours.

Compared with the prior art, the invention has the advantages that (1) the hard segment molecular chain segments (from anionic monomers and hydrophilic amide monomers) are introduced into the soft segment polysiloxane molecular structure (from carboxyl polysiloxane) through in-situ ester crosslinking reaction, and the soft segment and the hard segment cooperate to effectively improve the topological structure entropy of the synthetic polymer, thereby realizing the coordination between the cohesive force and the adhesive force of the synthetic polymer and realizing the excellent bonding effect of the modified polymer;

(2) The soft and hard segment synergistic modified polysiloxane polymer serving as a main film forming material has a molecular main chain still in a hydrophobic methyl siloxane structure, and meanwhile, the introduced hard segments are arranged at two ends of the molecular structure of the polymer, so that the cured coating still has excellent hydrophobicity, thereby maintaining low surface energy characteristics in the subsequent service process and having excellent antifouling effect;

(3) According to the invention, the modified polysiloxane polymer with excellent bonding effect is synthesized through simple in-situ transesterification, and meanwhile, the hard segment molecular structure is positioned at two ends of a polymer molecular chain, so that after the polymer is solidified and formed, the hard segment structure with excellent bonding effect is enriched in the area of the coating and the substrate through the movement of the molecular chain segment, the coating has firm bonding property, the soft segment structure with low surface energy is positioned on the surface of the coating, the excellent antifouling effect of the coating is ensured, and the coating is firmly bonded and has antifouling property through the molecular migration movement in the solidification process;

(4) The coating disclosed by the invention is applied to marine facility antifouling, is especially suitable for various marine facilities immersed in a seawater environment for a long time, has excellent antifouling property and is not easy to fall off.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the invention. These are all within the scope of the present invention.

According to the coating, the hard segment molecular structure with polarity and anion characteristics is grafted on the methyl siloxane of the soft segment, and the topological structure entropy of the methyl siloxane polymer is effectively improved through the synergistic effect of the soft segment and the hard segment, so that the coordination between the cohesive force and the adhesion force of the modified polymer is realized, and the modified polymer has an excellent bonding effect. The hard segment molecular structure is positioned at two ends of the modified polymer molecular chain, so that the damage of low surface energy of the cured coating caused by chemical modification is avoided, and the cured coating still has an excellent antifouling effect.

The soft and hard segment synergistic modified polysiloxane polymers 1 to 3 referred to in examples 1 to 5 were prepared by the following synthetic examples 1 to 3, respectively. The raw materials used in Synthesis examples 1 to 3 and examples 1 to 5 are shown in Table 1. The specific implementation is not limited to the raw materials in table 1, and the corresponding products can be selected according to the foregoing, and other raw materials used in the examples are all commercially available chemical reagents.

TABLE 1

Synthesis example 1

The weight ratio of the anionic monomer, the hydrophilic amide monomer, the carboxyl polysiloxane and the second solvent is 6:5:70:100. The specific preparation steps are as follows:

(1) Sequentially adding an anionic monomer 1-1, a hydrophilic amide monomer 2-2, carboxyl polysiloxane 3-1 and a second solvent 4-1 into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the PH to be more than 10 through a mixed solution of sodium hydroxide (1 g)/ethanol (10 g), and stirring at 50rpm for reaction for 16 hours at 40 ℃;

(2) The precipitated product after the reaction was filtered and washed at least 3 times with deionized water, followed by drying in a vacuum apparatus for 24 hours, to prepare soft and hard segment co-modified polysiloxane polymer 1.

Synthesis example 2

The weight ratio of the anionic monomer, the hydrophilic amide monomer, the carboxyl polysiloxane and the second solvent is 3:10:50:120. The specific preparation steps are as follows:

(1) Sequentially adding an anionic monomer 1-2, a hydrophilic amide monomer 2-1, carboxyl polysiloxane 3-1 and a second solvent 4-2 into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the PH to be more than 10 through a mixed solution of sodium hydroxide (1 g)/ethanol (10 g), and stirring at 20rpm for reaction for 10 hours at 45 ℃;

(2) The precipitated product after the reaction was filtered and washed at least 3 times with deionized water, followed by drying in a vacuum apparatus for 24 hours, to prepare soft and hard segment co-modified polysiloxane polymer 2.

Synthesis example 3

The weight ratio of the anionic monomer, the hydrophilic amide monomer, the carboxyl polysiloxane and the second solvent is 8:8:80:150. The specific preparation steps are as follows:

(1) Sequentially adding an anionic monomer 1-3, a hydrophilic amide monomer 2-3, carboxyl polysiloxane 3-2 and a second solvent 4-2 into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the PH to be more than 10 through a mixed solution of sodium hydroxide (1 g)/ethanol (10 g), and stirring at 20rpm for reaction for 10 hours at 45 ℃;

(2) The precipitated product after the reaction was filtered and washed at least 3 times with deionized water, followed by drying in a vacuum apparatus for 24 hours, to prepare soft and hard segment co-modified polysiloxane polymer 3.

Examples 1 to 5

Specific formulation ratios of the components of examples 1 to 5 are shown in Table 2

TABLE 2

According to table 2, a preparation method of the fouling release type marine antifouling paint with the soft and hard segment synergistic topological structure and the cured coating thereof in examples 1-5 comprises the following steps:

(1) Sequentially adding soft and hard segment synergistic modified polysiloxane polymer and auxiliary agent into dispersing stirring equipment, dispersing for 20min at 100rpm, adding pigment filler and first solvent into the dispersing stirring equipment, continuously dispersing for 20min at the same rotating speed, and preparing fouling release type marine antifouling paint with soft and hard segment synergistic topological structure, and then sealing and preserving;

(2) And (3) coating the coating by means of spraying, rolling coating, brushing and the like, and curing for at least 48 hours to prepare the coating with the thickness of 150-250 mu m.

The marine antifouling paint can be prepared by a conventional method of marine antifouling paint in practical application, and is not limited to the preparation method.

Comparative example 1 (common Silicone Low surface energy marine antifouling paint)

The common organosilicon low-surface-energy marine antifouling paint comprises the following raw materials, by weight, 90.0 parts of polysiloxane resin, 30.0 parts of pigment filler, 4.0 parts of cross-linking curing agent, 1.5 parts of catalyst, 0.5 part of auxiliary agent and 10.0 parts of third solvent.

The polysiloxane resin is alpha, omega-dihydroxypolydimethylsiloxane with 10000 mPa.s viscosity, the pigment is zinc oxide, the crosslinking curing agent is tetraethoxysilane, the catalyst is dibutyl tin dilaurate, the auxiliary agent is BYK161 dispersant of Pick company 0.5 part, and the third solvent is dimethylbenzene.

(1) 90.0 Parts of alpha, omega-dihydroxypolydimethylsiloxane with 10000 mPas viscosity and 30.0 parts of micron-sized zinc oxide are added into a dispersing machine, dispersed at a high speed for 30min at 300rpm, then 0.5 part of BYK161 dispersing agent of Pick company is added into the dispersing machine at 200rpm for 30min, and then the mixture is ground to a fineness less than 40 mu m through a sand mill to prepare pre-dispersed slurry, and the pre-dispersed slurry is canned for standby;

(2) Uniformly mixing 4.0 parts of ethyl orthosilicate and 10.0 parts of dimethylbenzene to prepare a cross-linking curing agent component, canning for later use, uniformly mixing 1.5 parts of dibutyltin dilaurate and 20.0 parts of dimethylbenzene to prepare a catalyst component, and canning for later use;

(3) Before use, the pre-dispersed slurry, the cross-linking curing agent component and the catalyst component are uniformly stirred according to the proportion, and the obtained coating is coated and cured to obtain the common organosilicon low-surface-energy marine antifouling coating with the thickness of 150-250 mu m.

Comparative example 2

In comparison with example 1, the modified polysiloxane polymer prepared without introducing an anionic monomer therein was prepared in the same manner as in example 1 except that the other components and parts by weight thereof were the same.

< Specific test experiments and conditions >

Test 1 surface free energy

The contact angles of deionized water and diiodomethane on the surface of the cured coating were measured using an XG-CAMC3 type full-automatic contact angle measuring instrument manufactured by Shanghai Xuan standard instruments, inc. The surface of the coating was cleaned with absolute ethanol and dried before measurement, and the free energy of the surface of the coating was then calculated according to the Owens two-liquid method.

Test 2 drawing method for measuring adhesion force (steel plate, epoxy intermediate paint) after soaking in seawater for 100 days

The adhesion of the coating applied to the corresponding substrate or epoxy intermediate paint was measured using a BGD500 digital display semiautomatic adhesion tester manufactured by precision instruments, inc. Before the steel plate is used, the steel plate needs to be polished by 800-mesh sand paper, and the used epoxy intermediate paint is epoxy cloud iron intermediate paint produced by Shanghai golden emperor. The test is carried out after soaking in sterilized seawater for 100 days, and then taking out and drying.

Test 3 antifouling Properties

A mixture containing at least 108 units of Streptococcus salivarius was dispersed in 20ml of tryptic soy broth and incubated in 5% CO2 at 38℃for 2 hours. The suspension was then further diluted and inoculated into agar supplemented with 5% sheep blood and incubated in 38 ℃,5% co2 for 48 hours, after which the units containing six colony forming units were dispersed in 10mL of tryptic soy broth. Subsequently 20mL of the above bacterial suspension was covered on a 10X 5cm range of coating and incubated in 38℃and 5% CO2 for 24 hours. After the completion of the incubation, each sample was subjected to a spin rinse in 45mL of distilled water for 30 seconds, and then rinsed with 50mL of distilled water to remove non-stick substances, and surface-adhered bacteria were observed using a Simga model 300 scanning electron microscope manufactured by Karl Seisaku corporation, germany.

The results of the specific test experiments of examples 1-5 and comparative examples 1-2 are shown in Table 3.

TABLE 3 Table 3

As can be seen from Table 3, examples 1 to 5 have lower free energy than comparative example 2, and can ensure that fouling organisms are difficult to adhere to the surface of the coating, so that the coating has good antifouling performance, and meanwhile, the adhesion force of examples 1 to 5 on steel plates and epoxy intermediate paints is more excellent than that of comparative example 1, so that the defect of poor adhesion between the paint and the substrate can be effectively overcome, and the coating can be firmly adhered to various substrates and intermediate paints. It can be confirmed from the above test that the examples have excellent antifouling effects while having good adhesion as compared with the comparative examples. Therefore, the coating disclosed by the invention is applied to marine facility antifouling, especially various marine facilities immersed in a seawater environment for a long time, can effectively inhibit adhesion of fouling organisms on the surface of the coating, and is not easy to peel after long-term use.

The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.

Claims (10)

1. The fouling release type marine antifouling paint with the soft and hard segment cooperative topological structure is characterized by comprising the following components in parts by weight:

The soft and hard segment synergistic modified polysiloxane polymer has a structure that main chain is hydrophobic methyl siloxane, and both ends are hard segment molecular chain segments from anionic monomers and hydrophilic amide monomers.

2. The fouling-release marine antifouling paint of a soft and hard segment synergistic topology according to claim 1, wherein the soft and hard segment synergistic modified polysiloxane polymer is prepared by the steps of:

(1) Sequentially adding an anionic monomer, a hydrophilic amide monomer, carboxyl polysiloxane and a second solvent into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the pH to be more than 10 through a sodium hydroxide/ethanol mixed solution, and stirring and reacting for 10-20 hours at 20-100 rpm under the condition of 40-50 ℃;

(2) Filtering the precipitate after the reaction, washing at least 3 times by using deionized water, and then drying in a vacuum device to obtain the soft and hard segment synergistic modified polysiloxane polymer.

3. The fouling release type marine antifouling paint with the soft and hard segment synergistic topological structure, which is disclosed in claim 2, is characterized in that the weight ratio of anionic monomer, hydrophilic amide monomer, carboxyl polysiloxane and solvent is (3-8): (5-10): (50-80): (100-150).

4. The fouling-release marine antifouling paint with a soft and hard segment synergistic topological structure according to claim 2, wherein the anionic monomer is selected from one of sodium 2-carboxyethylacrylate, sodium acrylate, sodium indolylacrylate and sodium alginate.

5. The fouling-release marine antifouling paint of a soft and hard segment synergistic topology according to claim 2, wherein the hydrophilic amide monomer is selected from one of N- (2-hydroxyethyl) acrylamide, methacrylamide and dimethylaminopropyl acrylamide.

6. The fouling-release marine antifouling paint with a soft and hard segment synergistic topological structure according to claim 2, wherein the carboxyl polysiloxane is selected from dicarboxyl-terminated polysiloxanes, and the viscosity of the dicarboxyl-terminated polysiloxanes is 2000-5000 mpa.s at room temperature.

7. The fouling-release marine antifouling paint of a soft and hard segment synergistic topology according to claim 2, wherein the second solvent is selected from one of ethanol, acetone and toluene.

8. The fouling-release marine antifouling paint with a soft and hard segment synergistic topological structure according to claim 1, wherein the auxiliary agent is at least one selected from wetting dispersant, defoamer and flatting agent.

9. The fouling-release marine antifouling paint of a soft and hard segment synergistic topology according to claim 1, wherein the first solvent is selected from one of methanol, xylene, acetone.

10. A method for preparing the fouling release type marine antifouling paint with the soft and hard segment cooperative topological structure as claimed in claim 1, which is characterized by comprising the following steps:

(1) Sequentially adding an anionic monomer, a hydrophilic amide monomer, carboxyl polysiloxane and a second solvent into reaction equipment which is protected by nitrogen and connected with a stirring reflux device, then adjusting the pH to be more than 10 through a sodium hydroxide/ethanol mixed solution, and stirring and reacting for 10-20 hours at 20-100 rpm under the condition of 40-50 ℃;

(2) Filtering the precipitate after reaction, washing at least 3 times by using deionized water, and then drying in a vacuum device to obtain the soft and hard segment synergistic modified polysiloxane polymer;

(3) Sequentially adding the soft and hard segment synergistic modified polysiloxane polymer and the auxiliary agent obtained in the step 2 into dispersing stirring equipment, adding pigment filler and first solvent into the dispersing stirring equipment after stirring and dispersing, continuously stirring and dispersing to obtain the fouling release type marine antifouling paint with the soft and hard segment synergistic topological structure, and then sealing and storing.