CN111234694B

CN111234694B - Antifouling material and preparation method thereof

Info

Publication number: CN111234694B
Application number: CN202010179450.7A
Authority: CN
Inventors: 蔺存国; 王利; 张金伟; 郑纪勇; 孙智勇
Original assignee: 725th Research Institute of CSIC
Current assignee: 725th Research Institute of CSIC
Priority date: 2020-03-16
Filing date: 2020-03-16
Publication date: 2021-07-27
Anticipated expiration: 2040-03-16
Also published as: CN111234694A

Abstract

The invention belongs to the technical field of marine organism fouling protection, and particularly relates to an antifouling material and a preparation method thereof, wherein the antifouling material comprises polydimethylsiloxane, a surface microstructure regulating component, a surface chemical property regulating component and a curing component, and the preparation method of the antifouling material comprises the following specific process steps: sequentially adding polydimethylsiloxane, a surface microstructure adjusting component, namely organic silicon resin containing an acrylonitrile structure and a surface chemical property adjusting component into a stirring kettle, grinding, adding a curing component to form a coating, and coating the coating diluted by dimethylbenzene on the surface of a substrate to obtain an antifouling material with multiple antifouling properties and a synergistic effect; the marine ecological environment antifouling paint does not use antifouling agents such as cuprous oxide, cuprous thiocyanate, organic tin and the like, has no destructive influence on the marine ecological environment, has an antifouling period of over 5 years, can be widely applied to surface marine organism pollution protection of marine engineering facilities and structures such as docks, drilling platforms, piers, piles and the like, and has good potential economic benefits.

Description

Antifouling material and preparation method thereof

The technical field is as follows:

the invention belongs to the technical field of marine organism fouling protection, and particularly relates to an antifouling material and a preparation method thereof.

Background art:

marine fouling organisms are a general term for microorganisms, plants and animals that grow on the bottom of ships and on the surface of all facilities in the sea. Marine antifouling coatings have undergone a process of development ranging from toxic to environmentally friendly, short term to long term. There are mainly 3 types of commercial antifouling coatings at present: firstly, the abrasion type antifouling paint is formed by adding cuprous oxide and other auxiliary antifouling agents into non-polishing film forming materials such as chlorinated rubber; secondly, a tin-free self-polishing antifouling coating is formed by adopting a copper/zinc/silicon acrylate self-polishing film forming material and cuprous oxide and other auxiliary antifouling agents; and thirdly, the fouling release type antifouling paint is formed by adopting the organic silicon elastomer as a film forming material and adding a surface energy regulator such as silicon oil. Cuprous oxide is widely applied to the first two materials at present, however, researches show that a large amount of copper element can be accumulated in a bay, so that serious damage is caused to the marine ecological environment, the antifouling period of the traditional antifouling paint based on heavy metals such as cuprous oxide and organic biocides is short, the requirement of a large ship for long dock repair interval cannot be met, and the serious damage is caused to the marine ecological environment, so that the development of environment-friendly and long-acting antifouling materials is imperative in the face of the trend of limited use or forbidden use. The fouling release type antifouling paint has long-acting antifouling performance, fouling organisms can be removed in the process of fast sailing of a ship, but the antifouling performance is poorer when the ship sails at low speed or is static, and the improvement of the low-speed sailing and static antifouling performance of the material is one of the development trends.

Research shows that the attachment density and the adhesive strength of larvae or spores of fouling organisms on the surface of a microstructure material with high regularity and proper size are greatly reduced. Brennan et al in the United states prepare the shark skin-imitated microstructure antifouling material by a laser etching and rollover method; the method for preparing the bionic dolphin skin material by microphase separation after blending two resins by Karen L.Wooley, Lenz et al obtain a microstructure antifouling material by copying a mussel shell; the raw material quality components of the preparation method of the antifouling material with the needle-shaped filler directionally arranged disclosed in the Chinese patent 201610184270.1 comprise 10-50 parts of self-polishing resin, 5-15 parts of rosin, 10-20 parts of main antifouling agent, 2-5 parts of auxiliary antifouling agent, 1-5 parts of pigment, 0.5-10 parts of needle-shaped filler, 0.5-5 parts of surfactant, 0.2-1 part of auxiliary agent and 3-15 parts of solvent; the preparation method comprises the following process steps: adding self-polishing resin, rosin, a main antifouling agent, an auxiliary antifouling agent, pigment, a surfactant and a solvent into a container in sequence according to a set mass part, ball-milling or stirring at a high speed for 2-24 hours, then adding an auxiliary agent and needle-shaped fillers into the container in sequence according to the set mass part, stirring for 1-3 hours to obtain an antifouling paint, coating the antifouling paint on the surface of a matrix, curing in a uniform magnetic field to form a film, and directionally arranging the needle-shaped fillers in a manner of following the direction of the magnetic field to prepare an antifouling material with the needle-shaped fillers in a directional arrangement manner; the self-polishing resin comprises polyacrylic resin, zinc polyacrylate resin, polyacrylic silane resin or polyacrylic copper resin; the main antifouling agent comprises cuprous oxide or cuprous thiocyanate; the auxiliary antifouling agent comprises zinc oxide, copper pyrithione, 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one, N-cyclopropyl-N' - (1, 1-dimethylethyl) -6- (methylthio) -1,3, 5-triazine-2, 4-diamine or zinc pyrithione; the pigment comprises carbon black, iron red, toluidine red, titanium white or a mixture of the above pigments; the needle-shaped filler is a permanent magnetic or instant magnetic filler and comprises needle-shaped gamma-Fe 3O4, Cr2O3 or nickel powder with the length-diameter ratio of more than 1.5; the surfactant comprises stearic acid, fatty glyceride, chlorinated paraffin, silicon ether or silicone oil; the auxiliary agent comprises silicon dioxide or polyacrylamide; the solvent comprises one or the mixture of ethyl acetate, N-butanol, toluene, xylene, N-dimethylformamide, dimethyl sulfoxide, acetylacetone and dimethyl carbonate; the self-adaptive microstructure anti-fouling and anti-drag material disclosed in Chinese patent 201410308738.4 is an organosilicon elastomer material, wherein the self-adaptive microstructure basic units are in a zigzag shape, the zigzag basic units are arranged at intervals in a staggered manner to form an array shape, the organosilicon elastomer material comprises an addition type organosilicon elastomer and a condensation type organosilicon elastomer, and an organosilicon surface microstructure is prepared by etching and mold turnover; the processing method of the microstructure in the preparation method of the antifouling material with the surface having the cross-shaped regular microstructure disclosed in the Chinese patent 201110376218.3 comprises the following steps: etching a microstructure with a cross pattern on a photomask by adopting an electron beam etching method, wherein the basic units are in a cross column shape, the tail ends are in a conical shape, and the basic units are arranged in a staggered manner to form an array; then, a plasma deep silicon etching process is adopted on the surface of the silicon wafer to form a microstructure with a specified depth: the height of the microstructure is 5-20 microns, the cross part is a protrusion, the distance is the distance from the top to the bottom of the cross, and the ratio of the protrusion area to the side wall area is 0.46-0.11; the cross-shaped part of the structure is a pit formed after etching; preparation of the antifouling material: flatly placing the silicon wafer, enabling the side with the microstructure to face upwards, and utilizing a disposable adhesive tape to sew and enclose the side to form an upper opening container with the silicon wafer as a bottom and the adhesive tape as a wall; then dripping polydimethylsiloxane liquid on the surface of the silicon wafer to ensure that the polydimethylsiloxane is paved on the surface of the silicon wafer; putting the mixture into a vacuum drier, and vacuumizing to remove bubbles; standing until the polydimethylsiloxane is cured, and uncovering the polydimethylsiloxane film from the edge after the polydimethylsiloxane film is completely cured at room temperature, so that the antifouling material with the surface having the cross-shaped regular microstructure can be formed on the surface of the polydimethylsiloxane material; the longest point of the microstructure cross is 15 micrometers, the cross width is 3 micrometers, and the basic unit interval is 3.4 micrometers; the above research or patented method is suitable for theoretical research and has difficulty in large-scale engineering application. Researches also find that the epidermis of large marine animal shark and the like can secrete and form a special hydrophilic mucus layer, and has obvious inhibition effect on the adsorption behavior of fouling organism adhesion protein. Significant progress has been made in the construction of biomimetic mucoid antifouling materials based on hydrophilic gels and amphiphilic polymers: the HEMPEL company has first introduced silicone antifouling coatings based on hydrogel technology, and international coatings company (IP) has also developed antifouling coatings with amphiphilic properties. However, the environmental-friendly antifouling coating prepared only through the surface microstructure, the low surface energy or the hydrophilic gel still faces the problem of poor antifouling performance under static state or low flow rate in the application process, and the coupling design of the multi-antifouling property is the main idea for solving the problem.

The invention content is as follows:

the invention aims to overcome the defects in the prior art and seek to design an antifouling material which takes Polydimethylsiloxane (PDMS) as a main material and is regulated and controlled by coupling of surface microstructure, surface chemical property and elastic modulus and a preparation method thereof.

In order to achieve the above object, the antifouling material according to the present invention comprises polydimethylsiloxane, a surface microstructure-adjusting component, a surface chemical property-adjusting component, and a curing component.

The polydimethylsiloxane related by the invention has the viscosity of 300-Hydroxy terminated polydimethylsiloxanes; the surface microstructure adjusting component consists of organic silicon resin containing an acrylonitrile structure and water-soluble organic amine, wherein the water-soluble organic amine comprises ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the water-soluble organic amine accounts for 1-3% of the antifouling material by mass; the surface chemical characteristic regulating component is prepared by the following two polymer chain segments in a molar ratio of 1: 10-10: 1, including polydimethylsiloxane-polyethylene glycol block copolymers (PDMS-PEG), polydimethylsiloxane-polyfluoro block copolymers (PDMS-PF), polydimethylsiloxane-polysulfonylbetaine block copolymers (PDMS-PSBMA), polydimethylsiloxane-polycarboxylic betaine block copolymers (PDMS-PCBMA), the block polymers being able to carry siloxy groups at both ends, for example: (RO)_1-3Si-PDMS-PEG-Si(OR)_1-3R is methyl, ethyl, propyl or propoxy, the surface chemical property adjusting component carrying the siloxy group can be anchored with the antifouling material main body through alkoxy, and the surface chemical property change caused by loss in the application process is avoided; the curing component is a compound formed by mixing one of stannous octoate, dibutyltin dilaurate or dibutyl diacetyltin with one of silicon 40, a silicon 40 modifier or trialkoxysilane, wherein the trialkoxysilane is trimethoxy silane and triethoxy silane, the trimethoxy silane comprises methyl trimethoxy silane, vinyl trimethoxy silane and aminopropyl trimethoxy silane, and the triethoxy silane comprises methyl triethoxy silane and vinyl triethoxy silane.

The specific process of the preparation method of the antifouling material comprises the following steps: adding 65-80 parts by mass of Polydimethylsiloxane (PDMS) and 5-30 parts by mass of a surface microstructure adjusting component-organic silicon resin containing an acrylonitrile structure into a stirring kettle in sequence, wherein the water-soluble organic amine accounts for 1-3% of the antifouling material by mass percent, adding 1-5 parts by mass of a surface chemical property adjusting component, grinding for 1-3h, adding 4-10 parts by mass of a curing component, rapidly dispersing to form a coating, using dimethylbenzene as a diluent and 1-20 parts by mass of the diluent, uniformly mixing the diluted coating, coating the surface of a substrate, and curing the coating to obtain the antifouling material with multiple antifouling properties and synergistic effect.

The antifouling material prepared by the invention takes polydimethylsiloxane as a main component; the surface microstructure adjusting component constructs a surface microstructure of the antifouling material under the self-assembly action of the resin molecular chain segment and the polar liquid drop in the film forming process; the surface chemical property regulating component is added into polydimethylsiloxane and organic silicon resin containing an acrylonitrile structure in a chemical anchoring or physical mixing mode to regulate and control the surface chemical property of the antifouling material; the curing component regulates and controls the characteristic modulus of the antifouling material through the crosslinking degree of the material, so that the regulation and control of the elastic characteristic of the antifouling material are realized.

The elastic modulus of the antifouling material prepared by the invention is 0.5-5MPa, and the elastic modulus is realized by changing the viscosity of polydimethylsiloxane and the types and the adding amount of curing components: for example, a higher viscosity (10000-; the antifouling material with higher elastic modulus can be prepared by adopting the polydimethylsiloxane with low viscosity (300-.

Compared with the prior art, the key point of the invention is that the raw material components are selected, and the compounding combination and the synergistic effect in the preparation process enable the antifouling material to simultaneously have elastic characteristics, surface microstructure and surface chemical characteristics, and show good antifouling and fouling release performances; determining that Polydimethylsiloxane (PDMS) is used as a main material, and preparing the antifouling material with the synergistic effect of multiple antifouling properties based on the self properties of the main material through the coupling regulation of a surface microstructure regulating component, a surface chemical property regulating component and a curing component; the method realizes the regulation and control of the elastic modulus by regulating and controlling the crosslinking density of the polymer, changes the stripping and releasing mode of fouling organisms, reduces the effective attachment area and the attachment strength of the fouling organisms, improves the static antifouling performance and the fouling release performance, does not use antifouling agents such as cuprous oxide, cuprous thiocyanate, organic tin and the like, almost has no consumption of main materials, utilizes the physicochemical characteristics of the surfaces of the main materials which are not beneficial to the adhesion of the organisms to prevent fouling, has no destructive influence on the marine ecological environment, has an antifouling period of over 5 years, meets the long-acting antifouling requirement of large ships, can be widely applied to the surface marine organism fouling protection of marine engineering facilities and structures such as docks, drilling platforms, piers, piles and the like, and has better potential economic benefit.

The specific implementation mode is as follows:

the invention is further described below by way of examples of implementation.

Example 1:

the specific process of the preparation method of the antifouling material related to the embodiment comprises the following steps: adding 80 parts by mass of hydroxyl-terminated polydimethylsiloxane with the viscosity of 300 centipoises, 5 parts by mass of organic silicon resin containing an acrylonitrile structure in a surface microstructure adjusting component and 5 parts by mass of front and rear polymer chain segments into a stirring kettle in sequence, wherein the molar ratio of the front polymer chain segment to the rear polymer chain segment is 1: 10 parts of trimethoxy polydimethylsiloxane-polyethylene glycol block copolymer (PDMS-PEG), grinding for 1 hour, adding 10 parts by mass of a compound formed by mixing stannous octoate and silicon 40 and water-soluble organic amine (tetraethylenepentamine) in the surface microstructure adjusting component, wherein the mass of the tetraethylenepentamine is 3% of the total mass of the antifouling material, quickly dispersing to form a coating, adding 1 part by mass of xylene, uniformly mixing and coating the coating on the surface of a base material, and curing the coating to obtain the antifouling material with multiple antifouling properties and synergistic effect.

Example 2:

the specific process of the preparation method of the antifouling material related to the embodiment comprises the following steps: adding 65 parts by mass of hydroxyl-terminated polydimethylsiloxane with the viscosity of 5000 centipoises, 30 parts by mass of organic silicon resin containing an acrylonitrile structure in the surface microstructure adjusting component and 1 part by mass of front and rear polymer chain segments into a stirring kettle in sequence, wherein the molar ratio of the front and rear polymer chain segments is 1: 1 dimethyl siloxane-polysulfonate betaine segmented copolymer (PDMS-PSBMA), grinding for 3h, adding 4 parts by mass of a compound formed by mixing stannous octoate and silicon 40 and water-soluble organic amine (ethylenediamine) in a surface microstructure adjusting component, wherein the mass of the ethylenediamine is 1% of the total mass of the antifouling material, quickly dispersing to form a coating, adding 10 parts by mass of xylene, uniformly mixing and coating the coating on the surface of a substrate, and curing the coating to obtain the antifouling material with multiple antifouling properties and synergism.

Example 3:

the specific process of the preparation method of the antifouling material related to the embodiment comprises the following steps: 75 parts by mass of hydroxyl-terminated polydimethylsiloxane with the viscosity of 150000 centipoise, 14 parts by mass of organic silicon resin containing an acrylonitrile structure in the surface microstructure adjusting component and 3 parts by mass of front and rear polymer chain segments are sequentially added into a stirring kettle, wherein the molar ratio of the front polymer chain segment to the rear polymer chain segment is 10: 1, grinding the block copolymer (PDMS-PF) with triethoxy polydimethylsiloxane-polyfluoride for 2h, adding 8 parts by mass of a compound formed by mixing dibutyltin dilaurate and triethoxysilane and a water-soluble organic amine (diethylenetriamine) in a surface microstructure adjusting component, wherein the mass of the diethylenetriamine is 2% of the total mass of the antifouling material, quickly dispersing to form a coating, adding 20 parts by mass of dimethylbenzene, uniformly mixing and coating the coating on the surface of a substrate, and curing the coating to obtain the antifouling material with multiple antifouling properties and synergistic effect.

Example 4:

the present example relates to performance evaluation of the antifouling materials prepared in examples 1, 2 and 3, and tests on the performance of the antifouling coatings of the antifouling materials prepared in examples 1, 2 and 3 are carried out in a coastal test station according to the national standard GB/T6822-2014 marine antifouling antirust paint system, GB/T5370-2007 antifouling paint sample plate shallow sea immersion test method and GB/T7789-2007 dynamic antifouling paint antifouling performance test method, and the test results show that the antifouling materials prepared in examples 1, 2 and 3 have good antifouling performance and the antifouling period is more than 5 years.

Claims

1. An antifouling material characterized by comprising 65 to 80 parts by mass of polydimethylsiloxane, 5 to 30 parts by mass of a surface microstructure-adjusting component, 1 to 5 parts by mass of a surface chemical property-adjusting component and 4 to 10 parts by mass of a curing component; the polydimethylsiloxane is hydroxyl-terminated polydimethylsiloxane with the viscosity of 300-; the surface microstructure adjusting component consists of organic silicon resin containing an acrylonitrile structure and water-soluble organic amine, wherein the water-soluble organic amine comprises ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the water-soluble organic amine accounts for 1-3% of the antifouling material by mass; the surface chemical characteristic regulating component is prepared by the following two polymer chain segments in a molar ratio of 1: 10-10: the block polymer 1 comprises a polydimethylsiloxane-polyethylene glycol block copolymer, a polydimethylsiloxane-polyfluoro block copolymer, a polydimethylsiloxane-polysulfonyl betaine block copolymer and a polydimethylsiloxane-polycarboxylic betaine block copolymer, wherein two ends of the block polymer can carry siloxy groups, and a surface chemical property adjusting component carrying siloxy groups can be anchored with an antifouling material main body through alkoxy groups, so that the surface chemical property change caused by loss in the application process is avoided; the curing component is a compound formed by mixing one of stannous octoate, dibutyltin dilaurate or dibutyl diacetyltin with one of silicon 40, a silicon 40 modifier or trialkoxysilane, wherein the trialkoxysilane is trimethoxy silane and triethoxy silane, the trimethoxy silane comprises methyl trimethoxy silane, vinyl trimethoxy silane and aminopropyl trimethoxy silane, and the triethoxy silane comprises methyl triethoxy silane and vinyl triethoxy silane.

2. The method for preparing the antifouling material according to claim 1, wherein the specific process comprises the following steps: sequentially adding polydimethylsiloxane and a surface microstructure adjusting component into a stirring kettle, adding a surface chemical property adjusting component, grinding for 1-3h, adding a curing component, quickly dispersing to form a coating, uniformly mixing the diluted coating with xylene as a diluent, wherein the using amount of the diluent is 1-20 parts by mass, coating the surface of a base material, and curing the coating to obtain an antifouling material with multiple antifouling properties and a synergistic effect; the prepared antifouling material takes polydimethylsiloxane as a main component; the surface microstructure adjusting component constructs a surface microstructure of the antifouling material under the self-assembly action of the resin molecular chain segment and the polar liquid drop in the film forming process; the surface chemical property regulating component is added into polydimethylsiloxane and organic silicon resin containing an acrylonitrile structure in a chemical anchoring or physical mixing mode to regulate and control the surface chemical property of the antifouling material; the curing component regulates and controls the characteristic modulus of the antifouling material through the cross-linking degree of the material, so as to realize the regulation and control of the elastic characteristic of the antifouling material; the elastic modulus of the prepared antifouling material is 0.5-5MPa, and the elastic modulus is realized by changing the viscosity of polydimethylsiloxane and the types and adding amounts of curing components.