CN115678394A - Functional marine long-acting antifouling paint - Google Patents
Functional marine long-acting antifouling paint Download PDFInfo
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- CN115678394A CN115678394A CN202211454521.5A CN202211454521A CN115678394A CN 115678394 A CN115678394 A CN 115678394A CN 202211454521 A CN202211454521 A CN 202211454521A CN 115678394 A CN115678394 A CN 115678394A
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Abstract
The invention relates to the technical field of marine antifouling paints, provides a functional marine long-acting antifouling paint, and solves the problems that the conventional marine antifouling paint only has a good dynamic antifouling effect and an unsatisfactory static antifouling effect. The functional marine long-acting antifouling paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 30-45 parts of polyurea resin, 10-20 parts of low molecular weight epoxy resin, 15-25 parts of organic silane resin, 1-10 parts of active bactericidal substance, 1-2 parts of dispersing agent, 3-5 parts of anti-settling agent, 5-10 parts of zinc oxide, 20-30 parts of pigment and 5-15 parts of diluent, wherein the component B is 20-30 parts by weight of isocyanate curing agent, and the component C is 3-5 parts by weight of ethyl silicate.
Description
Technical Field
The invention relates to the technical field of marine antifouling paints, in particular to a functional marine long-acting antifouling paint.
Background
Biofouling is a common problem of marine underwater facilities, and refers to biofouling formed by microorganisms, animals and plants in the sea, which are attached to the surface of marine engineering structures and continuously grow and multiply, and is commonly found at the bottom of ships and under the water surface of marine engineering structures.
The ship has the characteristics of long mooring (static) time, low navigation frequency, strong cross-sea region maneuverability, long voyage time and the like, and the marine biofouling phenomenon is particularly serious, thereby greatly influencing the navigation of the ship. The attachment amount of marine organisms on ships can reach as high as 80kg/m in the vigorous growing season 2 The speed of the ship can be reduced by 30%, and the maneuverability of the ship are seriously influenced. According to statistics, when the fouling area of the hull below the waterline reaches 5%, the fuel consumption is increased by 10%; when the fouling area reaches 10%, the fuel consumption is increased by 20%; when the fouling area is larger than 50%, the fuel consumption is increased by more than 40%. Under the condition of limited fuel, the self-sufficient force of the ship is greatly reduced. In addition, biofouling is also susceptible to the following adverse effects on ships: (1) The power system is overloaded for a long time, so that a fault occurs, and long-time parking and repair are needed; (2) The corrosion of metal equipment is accelerated, the service life of a ship steel plate is shortened, frequent periodic maintenance is required by manpower, the sailing rate of ships is influenced, and huge economic loss is generated.
The antifouling paint is the most effective, simple and economic means for solving the problem of biological fouling of ships. Antifouling agent releasing type coatings are the most widely used antifouling coatings at present. The antifouling paint mainly comprises antifouling resin, antifouling agent, pigment, filler, auxiliary agent, solvent and the like, wherein the most important components are the antifouling resin and the antifouling agent. The antifouling agent has the functions of dispelling and killing fouling organisms; the antifouling resin is a matrix of the antifouling paint, can control the release of the antifouling agent, and ensures the mechanical strength and the adhesiveness of the coating. Therefore, the quality of the resin properties directly determines the antifouling effect and the service life of the coating.
According to different resin types, the current commercial antifouling paint at home and abroad mainly comprises a matrix soluble type and a tin-free self-polishing type paint. The matrix resin of the matrix-soluble type antifouling paint is mainly rosin supplemented with a small amount of seawater-insoluble resin such as acrylic resin, chlorinated rubber, vinyl resin, epoxy resin and the like. When the antifouling paint is used, rosin is slowly dissolved in seawater, so that the thickness of the coating is gradually thinned along with the time lapse, the thickness of the escape layer cannot be obviously increased, the early-stage release amount of the antifouling agent is large, the later-stage decline cannot be too fast, and the problem of too short antifouling period is solved to a certain extent. Chinese patent No. CN201310723462.1 discloses a novel antifouling agent composite coating applied to a dissolving antifouling paint, which comprises the following components in parts by weight: 19.0 to 22.0 portions of rosin liquid, 13.0 to 15.0 portions of epichlorohydrin resin liquid, 0.4 to 0.5 portion of anti-settling agent, 2.0 to 3.0 portions of plasticizer, 2.0 to 3.0 portions of anti-sagging agent, 3.0 to 6.0 portions of zinc oxide, 2.0 to 3.2 portions of pigment, 35.0 to 45.0 portions of inorganic anti-fouling agent, 3.0 to 5.0 portions of organic anti-fouling agent and 5.0 to 7.0 portions of solvent. The coating is mainly applied to the protection of parts with marine organism fouling resistance requirements in the ship industry, has good antifouling performance, excellent environmental protection and low toxicity, and the released antifouling agent is quickly decomposed or degraded in seawater, so that the influence on the marine water body and fishes is less. However, rosin in the raw material of the matrix soluble antifouling paint is brittle and can not effectively prevent seawater from penetrating into the coating, so that a release layer is still thick (> 50 mu m), and various plasticizers and fillers are required to improve the mechanical property of the coating. When the rosin content is insufficient, the erosion rate and the release rate of the antifouling agent cannot meet the antifouling requirement; when the content of rosin is too large, the mechanical property of a coating film is poor, so that the regulation of the content of rosin is a key factor of the coating. The antifouling effect is unstable due to uncontrollable erosion rate of the coating, and the antifouling effect is poor in a static environment (erosion rate depends on the sailing speed of the ship). In addition, the rosin-based paint is not oxidation-resistant, and sealing protection is required after finishing coating or docking of a ship, and if the rosin-based paint is exposed in air and sunlight for a long time, the coating is easy to crack, so that the antifouling effect is influenced. Furthermore, erosion of the rosin leads to increased surface roughness and thus increased boat drag.
The companies Hairman (Hempel), zondon (Jotun), guanxi (Kansai), sigma (Sigma) and others were the earliest to research tin-free self-polishing antifouling paints and have in succession marketed a number of products, such as the Globic series of Hairman, seaQuan of Zondontum series, etc. The tin-free self-polishing antifouling paint uses low-toxicity copper, zinc, silicon and other elements to replace tin, and develops the tin-free self-polishing antifouling paint which uses polyacrylic acid copper, polyacrylic acid zinc and polyacrylic silane ester as base resin and uses low-toxicity cuprous oxide as an antifouling agent. Under the action of alkalescent seawater, the resin can become hydrophilic through hydrolysis of ester bonds, and can dissolve and fall off under the action of ship movement and seawater scouring, so that the surface is self-renewed, namely self-polishing. Simultaneous Cu in coating 2 O also releases Cu 2+ An effective antifouling thin layer is formed on the surface of the coating film, so that the coating film keeps smooth and antifouling property. For example, chinese patent No. CN201511017972.2 discloses a self-polishing antifouling paint and a preparation method thereof, wherein 100 parts by mass of the antifouling paint comprises the following components: 18-24 parts of resin, 50-55 parts of antifouling agent, 0.5-1.5 parts of graphene microchip, 3-6 parts of pigment and filler, 1-2 parts of dispersant, 1-2 parts of organic bentonite and the balance of organic solvent; wherein the resin consists of hydroxy acrylic resin, zinc acrylate resin and rosin; the antifouling agent consists of copper pyrithione, 4, 5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, cuprous oxide and zinc oxide. The obtained self-polishing antifouling paint has stable product quality, long antifouling period, good polishing, high strength, cracking resistance and low VOC.
In the self-polishing antifouling paints, the copper polyacrylate and the zinc polyacrylate-based resin are subjected to ion exchange with seawater, so that the hydrolysis speed is high, the controllability is poor, the environmental adaptability is poor, and the conditions of high hydrolysis speed in the early stage and low hydrolysis speed in the later stage are usually caused. The polyacrylic silane ester resin forms sodium salt through lateral group hydrolysis, has slow and stable hydrolysis characteristics, is the only chemical bond at present, can keep the hydrolysis state for a long time, can control the hydrolysis rate, and can realize long-term update of a coating and sustained release of an antifouling agent. Thus, silane ester based antifouling techniques are the best choice to achieve long lasting antifouling. The most advanced antifouling paints in the world today are also based on this technology, such as SeaQuantum series by the company zondon (Jotun), interssmooth 7475Si by the company International Paints (IP), etc. However, the self-polishing antifouling coating takes the polyacrylic silane ester as the matrix resin, only the side group can be hydrolyzed, the hydrolysis rate depends on the washing of water flow seriously, and the sodium salt of the polymer generated by hydrolysis cannot be dissolved in time due to lack of strong water flow washing in static state or low navigational speed, so that the resin polishing rate is low, the release rate of the antifouling agent is also low, and finally the antifouling effect is not ideal. Therefore, when a ship sails at a low speed or stops sailing, the coating only depends on seawater self-flow, the ideal self-polishing effect is difficult to achieve, the coating is easy to lose efficacy, once fouling organisms are adhered, the coating cannot be polished or an antifouling agent is released, and the antifouling period is limited. In addition, the main chain structure of the polyacrylic silane ester resin is a stable C-C structure, the polyacrylic silane ester resin is difficult to degrade in seawater, and the resin exists in the marine environment for a long time, so that the marine micro plastic pollution is caused. The problems of physical damage in vivo, change of eating behavior, reduction of reproductive capacity and the like can occur after marine organisms eat the micro-plastic by mistake.
Disclosure of Invention
Therefore, in view of the above, the present invention provides a functional marine long-lasting antifouling paint, which solves the problems that the existing marine antifouling paint only has good dynamic antifouling effect and the static antifouling effect is not ideal.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a functional marine long-acting antifouling paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 30-45 parts of polyurea resin, 10-20 parts of low molecular weight epoxy resin, 15-25 parts of organic silane resin, 1-10 parts of active bactericidal substance, 1-2 parts of dispersing agent, 3-5 parts of anti-settling agent, 5-10 parts of zinc oxide, 20-30 parts of pigment and 5-15 parts of diluent, wherein the component B is 20-30 parts by weight of isocyanate curing agent, the component C is 3-5 parts by weight of ethyl silicate, and the structural formula of the polyurea resin is shown as the formula I:
wherein R is 1 ，R 2 Each independently represents C 8 ～C 10 N is a value in the range of 2 to c4;
the structural formula of the organosilane resin is shown as a formula II:
wherein R is 3 ，R 4 Each independently represents C 5 ～C 20 P is an integer ranging from 2 to 4, q is an integer ranging from 3 to 6.
The further improvement is that: the diluent is formed by mixing dimethylbenzene and butyl acetate, wherein the mass fraction of the dimethylbenzene is 60-80%, and the mass fraction of the butyl acetate is 20-40%.
The further improvement is that: the active bactericidal substance is dexmedetomidine.
The further improvement is that: the low molecular weight epoxy resin is bisphenol A type epoxy resin, and the molecular weight range is 200-400.
The further improvement is that: the component A, the component B and the component C are uniformly stirred and mixed according to the mass ratio of 17.5.
The further improvement is that: the component A is prepared by the following steps:
(1) Weighing the raw materials according to the predetermined weight part for later use;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is completely dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organic silane resin, stirring for 20-30 min, then heating to 90-110 ℃, preserving heat for 1-3 h, then adding active sterilizing substances, stirring for 10-20 min, stopping stirring, cooling to 50-70 ℃, preserving heat for 1-3 h, and obtaining modified resin;
(3) Adding the modified resin into a stirring device, adding the dispersing agent and the anti-settling agent, stirring and mixing uniformly, adding the zinc oxide and the pigment, stirring and mixing for 20-40 min, adding the diluent to adjust the viscosity, grinding until the fineness is less than 60 mu m, filtering after the detection is qualified, and packaging to obtain the component A.
By adopting the technical scheme, the invention has the beneficial effects that:
according to the functional marine long-acting antifouling paint provided by the application, in the preparation process of the component A, firstly, an epoxy group of epoxy resin reacts with a small part of terminal amino groups of polyurea resin to obtain an intermediate product, and the different characteristics of the two resins are utilized, so that the adhesion and toughness of a coating formed after the antifouling paint is constructed are improved; secondly, adding organosilane resin with a main chain of hydroxyl-terminated organosilicon and a side chain of polyether, and chemically grafting the organosilane resin with an intermediate product to form a specific functional group with a main chain of hydrophobic side chain and hydrophilic property; finally, the active sterilization substance is grafted to the specific functional group through a chemical grafting reaction to obtain a high polymer with the sterilization active substance, namely modified resin.
During construction, the component A, the component B and the component C are stirred for 3-5 min according to the proportion, are uniformly mixed and then stand for 5min, and are sprayed on the surface of an object to be subjected to antifouling treatment to form an antifouling coating. The isocyanate group of the component B and the terminal amino group in the molecular structure of the modified resin in the component A are reacted and crosslinked; the component C, ethyl silicate reacts with terminal hydroxyl of a main chain in a molecular structure of the modified resin to form a space network structure with a low surface, and polyether of a side chain is hydrophilic, so that an elastic hydrogel paint film is formed between the surface of the coating and seawater. The marine long-acting antifouling paint prepared by the invention has extremely high elasticity and super toughness, and a coating formed after spraying has very good expansion and contraction rate. When the ship is in a dynamic state, the paint film can play a role of shrinking according to the speed of water flow, so that marine organisms are difficult to attach; and the active bactericidal substance is matched, so that the marine organisms can easily fall off even if attached. When the antifouling paint is applied to static conditions such as net cages, ocean facilities, seawater pipelines and the like, the active bactericidal substances in the coating actively float on the surface of the coating due to the hydrophobic function of the surface of the coating and the elastic hydrogel paint film formed by the surface of the coating and seawater, so that marine organisms are effectively killed, and the adhesion of the ocean is prevented.
In a word, the marine long-acting antifouling paint prepared by the invention has double functions of static antifouling and dynamic antifouling, and has good antifouling effect under both dynamic and static conditions. Compared with the existing hydrolysis type self-polishing antifouling material, the hydrolysis type self-polishing antifouling material has wider performance regulation range and wider application range, and particularly, the performance of the hydrolysis type self-polishing antifouling material does not depend on the ship speed and the ship period.
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagent used are indicated at the first appearance.
Example 1
A functional marine long-acting antifouling paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 35 parts of polyurea resin, 20 parts of low-molecular-weight bisphenol A epoxy resin, 25 parts of organic silane resin, 5 parts of dexmedetomidine, 2 parts of dispersing agent, 4 parts of polyamide wax anti-settling agent, 10 parts of zinc oxide, 20 parts of iron oxide red and 15 parts of diluent, wherein the diluent is prepared by mixing xylene and butyl acetate according to a mass ratio of 60;
the structural formula of the polyurea resin is shown as the formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 8 carbon atoms, and n takes a value of 2;
the structural formula of the organosilane resin is shown as the formula II:
wherein R is 3 ，R 4 Each independently represents an alkylene group having 10 carbon atoms, p has a value of 2, and q has a value in the range of 4.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to the predetermined weight part for later use;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is completely dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 20min, then heating to 100 ℃, preserving heat for 2h, then adding active sterilizing substances, stirring for 10min, stopping stirring, cooling to 60 ℃, preserving heat for 2h, and obtaining modified resin;
(3) Adding the modified resin into a stirring device, adding the dispersing agent and the anti-settling agent, stirring and mixing uniformly, adding the zinc oxide and the pigment, stirring and mixing for 20min, adding the diluent to adjust the viscosity, grinding until the fineness is less than 60 mu m, filtering after the detection is qualified, and packaging to obtain the component A.
And stirring the component A, the component B and the component C for 3-5 min, uniformly mixing, and standing for 5min to obtain the marine long-acting antifouling paint. The marine long-lasting antifouling paint prepared in the embodiment is subjected to performance detection, and the test results are shown in tables 1 and 2.
TABLE 1
TABLE 2
As can be seen from tables 1-2, the marine long-acting antifouling paint prepared by the embodiment has good adhesion, is easy to construct, and has excellent static and dynamic antifouling effects.
Antifouling performance tests were carried out using a commercially available matrix-soluble antifouling paint as comparative example 1, self-polishing antifouling paint a (using zinc polyacrylate as a matrix resin) as comparative example 2, and self-polishing antifouling paint B (using polysilazane polyacrylate as a matrix resin) as comparative example 3, and the results are shown in table 3.
TABLE 3
As can be seen from Table 3, the marine antifouling paint prepared by the invention has good static antifouling and dynamic antifouling effects, and is superior to the existing antifouling paint products.
Example 2
A functional marine long-acting antifouling paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 30 parts of polyurea resin, 15 parts of low-molecular-weight bisphenol A epoxy resin, 20 parts of organic silane resin, 1 part of dexmedetomidine, 1 part of dispersing agent, 3 parts of polyamide wax anti-settling agent, 5 parts of zinc oxide, 30 parts of iron oxide red and 10 parts of diluent, wherein the diluent is prepared by mixing xylene and butyl acetate according to a mass ratio of 70; the component B is 25 parts by weight of HDI curing agent (model N3375 curing agent manufactured by Bayer company), and the component C is 3 parts by weight of ethyl silicate;
the structural formula of the polyurea resin is shown as the formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 9 carbon atoms, and n is 3;
the structural formula of the organosilane resin is shown as a formula II:
wherein R is 3 ，R 4 Each independently represents an alkylene group having 5 carbon atoms, p is 3, and q is in the range of 5.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to the predetermined weight part for later use;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is completely dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 25min, then heating to 90 ℃, keeping the temperature for 3h, then adding active sterilizing substances, stirring for 15min, stopping stirring, cooling to 50 ℃, keeping the temperature for 3h, and obtaining modified resin;
(3) Adding the modified resin into a stirring device, adding the dispersing agent and the anti-settling agent, stirring and mixing uniformly, adding the zinc oxide and the pigment, stirring and mixing for 30min, adding the diluent to adjust the viscosity, grinding until the fineness is less than 60 mu m, filtering after the detection is qualified, and packaging to obtain the component A.
The marine antifouling paint prepared by the embodiment is subjected to performance test, and the test result is equivalent to the test result of the embodiment 1.
Example 3
A functional marine long-acting antifouling paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 45 parts of polyurea resin, 10 parts of low-molecular-weight bisphenol A epoxy resin, 15 parts of organic silane resin, 10 parts of dexmedetomidine, 1.5 parts of dispersing agent, 5 parts of polyamide wax anti-settling agent, 8 parts of zinc oxide, 25 parts of iron oxide red and 5 parts of diluent, wherein the diluent is prepared by mixing xylene and butyl acetate according to a mass ratio of 80; the component B is HDI curing agent 30 parts by weight (model HT100 curing agent produced by Wanhua chemical Co., ltd.), and the component C is ethyl silicate 5 parts by weight;
the structural formula of the polyurea resin is shown as the formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 10 carbon atoms, and n takes a value of 4;
the structural formula of the organosilane resin is shown as a formula II:
wherein R is 3 ，R 4 Each independently represents an alkylene group having 20 carbon atoms, p is 4, and q is in the range of 6.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to the predetermined weight part for later use;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is completely dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 30min, then heating to 110 ℃, preserving heat for 1h, then adding active sterilizing substances, stirring for 20min, stopping stirring, cooling to 70 ℃, preserving heat for 1h, and obtaining modified resin;
(3) Adding the modified resin into a stirring device, adding the dispersing agent and the anti-settling agent, stirring and mixing uniformly, adding the zinc oxide and the pigment, stirring and mixing for 40min, adding the diluent to adjust the viscosity, grinding until the fineness is less than 60 mu m, filtering after the detection is qualified, and packaging to obtain the component A.
The marine long-lasting antifouling paint prepared in the embodiment is subjected to performance test, and the test result is equivalent to that of the embodiment 1.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (5)
1. A functional marine long-acting antifouling paint is characterized in that: the paint consists of a component A, a component B and a component C, wherein the component A comprises the following raw materials in parts by weight: 30-45 parts of polyurea resin, 10-20 parts of low molecular weight epoxy resin, 15-25 parts of organic silane resin, 1-10 parts of active bactericidal substance, 1-2 parts of dispersing agent, 3-5 parts of anti-settling agent, 5-10 parts of zinc oxide, 20-30 parts of pigment and 5-15 parts of diluent, wherein the component B is 20-30 parts by weight of isocyanate curing agent, the component C is 3-5 parts by weight of ethyl silicate, and the structural formula of the polyurea resin is shown as the formula I:
wherein R is 1 ，R 2 Each independently represents C 8 ～C 10 N is an integer ranging from 2 to 4;
the structural formula of the organosilane resin is shown as a formula II:
wherein R is 3 ，R 4 Each independently represents C 5 ～C 20 P is an integer ranging from 2 to 4, q is an integer ranging from 3 to 6.
2. The functional marine antifouling paint as claimed in claim 1, wherein: the diluent is formed by mixing dimethylbenzene and butyl acetate, wherein the mass fraction of the dimethylbenzene is 60-80%, and the mass fraction of the butyl acetate is 20-40%.
3. The functional marine antifouling paint as claimed in claim 1, wherein: the active bactericidal substance is dexmedetomidine.
4. The functional marine long-lasting antifouling paint according to claim 1, wherein: the low molecular weight epoxy resin is bisphenol A type epoxy resin, and the molecular weight range is 200-400.
5. The functional marine antifouling paint as claimed in claim 1, wherein: the component A is prepared by the following steps:
(1) Weighing the raw materials according to the predetermined weight part for later use;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is completely dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 20-30 min, then heating to 90-110 ℃, preserving heat for 1-3 h, then adding active sterilizing substances, stirring for 10-20 min, stopping stirring, cooling to 50-70 ℃, preserving heat for 1-3 h, and obtaining modified resin;
(3) Adding the modified resin into a stirring device, adding the dispersing agent and the anti-settling agent, stirring and mixing uniformly, adding the zinc oxide and the pigment, stirring and mixing for 20-40 min, adding the diluent to adjust the viscosity, grinding until the fineness is less than 60 mu m, filtering after the detection is qualified, and packaging to obtain the component A.
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| CN113773436A (en) * | 2021-09-16 | 2021-12-10 | 青岛科技大学 | Amphiphilic organic silicon coating and preparation method and application thereof |
| CN115162025A (en) * | 2022-07-22 | 2022-10-11 | 潍坊佳诚数码材料有限公司 | Digital inkjet camouflage net and preparation method thereof |
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