CN115678394B - Functional marine long-acting antifouling paint - Google Patents
Functional marine long-acting antifouling paint Download PDFInfo
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- CN115678394B CN115678394B CN202211454521.5A CN202211454521A CN115678394B CN 115678394 B CN115678394 B CN 115678394B CN 202211454521 A CN202211454521 A CN 202211454521A CN 115678394 B CN115678394 B CN 115678394B
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Abstract
The application relates to the technical field of marine antifouling paint, provides functional marine long-acting antifouling paint, and solves the problems that the conventional marine antifouling paint only has good dynamic antifouling effect and the static antifouling effect is not ideal. 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 organosilane 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 of isocyanate curing agent by weight, and the component C is 3-5 parts of ethyl silicate by weight.
Description
Technical Field
The application relates to the technical field of marine antifouling paint, in particular to functional marine long-acting antifouling paint.
Background
Biofouling is a common problem of marine underwater facilities, and is a biological scale formed by attachment of microorganisms, animals and plants in the ocean to the surface of a marine engineering structure and continuous growth and propagation, and is commonly found at the bottom of a ship and below the water surface of the marine engineering structure.
The ship has the characteristics of long berthing (static state) time, low sailing frequency, strong maneuverability across sea areas, long voyage time and the like, and the marine biofouling phenomenon is particularly serious, so that the sailing of the ship is greatly influenced. In the growing season, the attachment amount of marine organisms on ships can reach 80kg/m 2 Resulting in 30% decrease in speed and serious impact on maneuverability and handling. 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 it is dirtyThe loss area is larger than 50%, and the fuel consumption is increased by more than 40%. Under the condition of limited fuel, the self-power of the ship is greatly reduced. In addition, biofouling is also prone to cause the following adverse effects on ships: (1) The power system is operated in overload for a long time, so that faults occur, and long-time navigation stopping repair is 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 a ship is influenced, and huge economic loss is generated.
The application of the antifouling paint is the most effective, simple and economical means for solving the ship biofouling problem. The anti-fouling agent releasing paint is the most widely used anti-fouling paint at present. The antifouling paint mainly comprises antifouling resin, an antifouling agent, pigment, filler, an auxiliary agent, a solvent and the like, wherein the most critical components are the antifouling resin and the antifouling agent. The antifouling agent has the functions of dispersing and killing fouling organisms; the antifouling resin is a matrix of the antifouling paint, so that not only can release of the antifouling agent be controlled, but also the mechanical strength and the adhesiveness of the coating are ensured. Therefore, the quality of the resin performance directly determines the antifouling effect and the service life of the paint.
According to different types of resin, the current commercial antifouling paint mainly comprises a matrix soluble type tin-free self-polishing paint. The matrix resin of the matrix soluble type antifouling paint is mainly rosin and is supplemented with a small amount of seawater insoluble resin, such as acrylic resin, chlorinated rubber, vinyl resin, epoxy resin and the like. When the anti-fouling agent is used, rosin is slowly dissolved in seawater, so that the thickness of a coating gradually becomes thinner along with the time, and the thickness of an escape layer cannot be obviously increased, so that the early release amount of the anti-fouling agent is large, the later decline cannot be too fast, and the problem of too short anti-fouling effect is solved to a certain extent. Chinese patent No. CN201310723462.1 discloses a novel antifouling agent combination coating applied to a soluble type antifouling paint, comprising the following components in parts by weight: 19.0 to 22.0 parts of rosin liquid, 13.0 to 15.0 parts of chloroether resin liquid, 0.4 to 0.5 part of anti-settling agent, 2.0 to 3.0 parts of plasticizer, 2.0 to 3.0 parts of anti-sagging agent, 3.0 to 6.0 parts of zinc oxide, 2.0 to 3.2 parts of pigment, 35.0 to 45.0 parts of inorganic anti-fouling agent, 3.0 to 5.0 parts of organic anti-fouling agent and 5.0 to 7.0 parts of solvent. The coating is mainly applied to the marine biofouling resistant part protection in the ship industry, has good antifouling property, excellent environmental protection and low toxicity, and the released antifouling agent is quickly decomposed or degraded in seawater, so that the influence on the water body and fish of the ocean is smaller. However, rosin in the raw materials of the matrix soluble antifouling paint is brittle, seawater cannot be effectively prevented from penetrating into the coating, an escape layer is still thicker (> 50 mu m), and various plasticizers and fillers are required to be added to improve the mechanical properties of the coating. When the rosin content is insufficient, the corrosion rate and the release rate of the anti-fouling agent cannot meet the anti-fouling requirement; when the rosin content is too much, the mechanical properties of the coating film become poor, so that the regulation of the rosin content is a key factor of such a coating. Since the erosion rate of such coatings is not controllable, the antifouling effect is unstable and poor in static environments (erosion rate depends on the sailing rate of the ship). In addition, rosin-based paint is not oxidation-resistant, and sealing protection is carried out after finishing coating or docking, if the rosin-based paint is exposed to air and sunlight for too long, the coating is easy to crack, so that the antifouling effect is affected. Furthermore, corrosion of rosin causes an increase in surface roughness, thereby increasing the resistance to boat travel.
Companies such as sea irides (Hempel), london (Jotun), guan xi (Kansai), sigma (Sigma) and the like have first studied tin-free self-polishing antifouling paints, and have successively been brought to market a large number of products such as the Globic series of sea irides, the SeaQuantum series of london and the like. The tin is replaced by low-toxicity copper, zinc, silicon and other elements, and tin-free self-polishing antifouling paint which takes copper polyacrylate, zinc polyacrylate and polysilicates as base resin and low-toxicity cuprous oxide as an antifouling agent is developed. Under the action of weak alkaline seawater, the resin can become hydrophilic through the hydrolysis of ester bonds, and the resin is dissolved and falls off under the action of ship movement and seawater scouring, so that the self-renewal of the surface, namely 'self-polishing', is achieved. While Cu in the coating 2 O also releases Cu 2+ An effective thin antifouling layer is formed on the surface of the paint film, so that the paint film keeps smooth and antifouling. 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 self-polishing antifouling paint is covered withComprises the following components: 18-24 parts of solid 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 dispersing agent, 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-isothiazolin-3-one, cuprous oxide and zinc oxide. The self-polishing antifouling paint product has stable quality, long antifouling period, good polishing, high strength, cracking resistance and low VOC.
In the self-polishing antifouling paint, 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 suitability is poor, and the conditions of high early hydrolysis speed and low later hydrolysis speed are often generated. The polysilicates are hydrolyzed to form sodium salt through side groups, have slow and stable hydrolysis characteristics, are the only chemical bond capable of keeping the hydrolysis state for a long time and controlling the hydrolysis rate at present, and can realize long-term update of the coating and continuous release of the anti-fouling agent. Thus, silane ester based antifouling technology is the best choice for achieving long lasting antifouling. The most advanced anti-fouling paint internationally at present is also based on this technology, such as SeaQuantum series from the company Zoton (Jotun), intersmooth 7475Si from the company International Paint (IP), etc. However, the self-polishing antifouling paint uses the polysilicates as matrix resin, only the side groups can be hydrolyzed, the hydrolysis rate is seriously dependent on the flushing of water flow, and when the self-polishing antifouling paint is static or low in navigational speed, strong water flow flushing is absent, polymer sodium salt generated by hydrolysis cannot be dissolved in time, so that the resin polishing rate is lower, the release rate of an antifouling agent is lower, and finally, the antifouling effect is unsatisfactory. Therefore, when the ship sails at a low speed or stops sailing, the coating is difficult to achieve an ideal self-polishing effect by means of sea water self-flowing, is easy to fail, and once fouling organisms adhere, the coating cannot polish or release an anti-fouling agent, so that the anti-fouling period is limited. In addition, the main chain structure of the polysilicates is a stable C-C structure, so that the polysilicates are difficult to degrade in seawater, and the polysilicates are long-term in the marine environment, so that marine microplastic pollution is caused. Problems such as physical damage in vivo, change of feeding behavior, reduction of reproductive capacity and the like can occur after marine organisms eat the microplastic by mistake.
Disclosure of Invention
Therefore, aiming at the above, the application provides the functional marine long-acting antifouling paint, which solves the problems that the conventional marine antifouling paint only has good dynamic antifouling effect and the static antifouling effect is not ideal.
In order to achieve the above purpose, the application is realized by the following technical scheme:
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 organosilane 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 of isocyanate curing agent, the component C is 3-5 parts of ethyl silicate, and the structural formula of the polyurea resin is shown as 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 having a value in the range of 2 to 4, and q is an integer having a value in the range of 3 to 6.
The further improvement is that: the diluent is formed by mixing dimethylbenzene and butyl acetate, wherein the dimethylbenzene accounts for 60-80% by mass, and the butyl acetate accounts for 20-40% by mass.
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 stirred and mixed uniformly according to the mass ratio of 17:2.5:0.5, so that the functional marine long-acting antifouling paint is formed.
The further improvement is that: the component A is prepared by the following steps:
(1) Weighing the raw materials according to preset weight parts for standby;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is thoroughly dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 20-30 min, heating to 90-110 ℃, preserving heat for 1-3 h, then adding active bactericidal substances, stirring for 10-20 min, stopping stirring, cooling to 50-70 ℃, and preserving heat for 1-3 h to obtain modified resin;
(3) Adding the modified resin into a stirring device, adding a dispersing agent and an anti-settling agent, stirring and mixing uniformly, adding zinc oxide and pigment, stirring and mixing for 20-40 min, adding a diluent to adjust viscosity, grinding to fineness less than 60 mu m, filtering and packaging after detection is qualified, thus obtaining the component A.
By adopting the technical scheme, the application has the beneficial effects that:
in the preparation process of the component A, firstly, epoxy groups of epoxy resin and small part of terminal amino groups of polyurea resin react to obtain an intermediate product, and the adhesive force and toughness of a coating formed after the construction of the antifouling paint are increased by utilizing different characteristics of the two resins; secondly, adding organosilane resin with a main chain of hydroxyl-terminated organosilicon and a side chain of polyether, and performing chemical grafting with an intermediate product to form a specific functional group with a main chain of hydrophobic side chain and hydrophilic side chain; and finally, the active bactericidal substance is connected to the specific functional group through a chemical grafting reaction, so that the polymer with the bactericidal active substance, namely the modified resin, is obtained.
During construction, the component A, the component B and the component C are stirred for 3-5 min according to the proportion, and the mixture is kept stand for 5min after being uniformly mixed, and sprayed on the surface of an object to be treated with the anti-fouling coating. The isocyanate group of the component B reacts with the terminal amino group in the molecular structure of the modified resin in the component A to crosslink; the C component ethyl silicate reacts with terminal hydroxyl groups of a main chain in the molecular structure of the modified resin to form a space network structure with a low surface, and the polyether with side chains is hydrophilic, so that a layer of elastic hydrogel paint film is formed between the surface of the coating and seawater. The marine long-acting antifouling paint prepared by the application has extremely high elasticity and super toughness, and a coating formed after spraying has very good expansion rate. When the ship is in a dynamic condition, the paint film can play a role in shrinkage according to the speed of water flow, so that marine organisms are difficult to attach; and then the active bactericidal substances are matched, so that the marine organism is easy to fall off even if attached. When the antifouling paint is applied to static conditions such as net cages, marine facilities, seawater pipelines and the like, the surface of the coating has a hydrophobic function, and the surface of the coating and seawater form an elastic hydrogel paint film, so that active bactericidal substances in the coating float on the surface of the coating very actively, 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 application has double functions of static antifouling and dynamic antifouling, and has good antifouling effects under dynamic and static conditions. Compared with the existing hydrolysis type self-polishing antifouling material, the material has wider performance regulation range and wider application range, and particularly, the performance of the material is independent of the speed and the period of the ship.
Detailed Description
The following describes embodiments of the present application in detail with reference to specific examples, so as to solve the technical problem by applying the technical means to the present application, and the implementation process for achieving the technical effect can be fully understood and implemented accordingly.
Unless otherwise indicated, the technical means employed in the examples are conventional means well known to those skilled in the art, and the reagents and products employed are also commercially available. The sources of the reagents used, the trade names and the members of the list of constituents which are necessary are all indicated at the first occurrence.
Example 1
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: 35 parts of polyurea resin, 20 parts of low molecular weight bisphenol A type epoxy resin, 25 parts of organosilane 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 dimethylbenzene and butyl acetate according to a mass ratio of 60:40, the epoxy resin adopts Nanya brand E20 epoxy resin, the component B is 20 parts by weight of HDI curing agent (model N3390 curing agent manufactured by Bayer corporation), and the component C is 4 parts by weight of ethyl silicate;
the structural formula of the polyurea resin is shown as formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 8 carbon atoms, and n has a value of 2;
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 10 carbon atoms, p has a value of 2, and q has a value of 4.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to preset weight parts for standby;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is thoroughly dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 20min, then heating to 100 ℃, preserving heat for 2h, adding active bactericidal substances, stirring for 10min, stopping stirring, cooling to 60 ℃, and preserving heat for 2h to obtain modified resin;
(3) Adding the modified resin into a stirring device, adding a dispersing agent and an anti-settling agent, stirring and mixing uniformly, adding zinc oxide and pigment, stirring and mixing for 20min, adding a diluent to adjust viscosity, grinding to fineness less than 60 mu m, filtering and packaging after detection is qualified, thus obtaining the component A.
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-acting 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 in the embodiment has good adhesion, is easy to construct, and has excellent static and dynamic antifouling effects.
The results of the antifouling performance test were shown in table 3 using a commercially available base-soluble antifouling paint as comparative example 1, a self-polishing antifouling paint a (using zinc polyacrylate as a base resin) as comparative example 2, and a self-polishing antifouling paint B (using polysilanoate as a base resin) as comparative example 3.
TABLE 3 Table 3
As can be seen from Table 3, the marine antifouling paint prepared by the application has good static antifouling and dynamic antifouling effects and is superior to the existing antifouling paint products.
Example 2
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 parts of polyurea resin, 15 parts of low molecular weight bisphenol A type epoxy resin, 20 parts of organosilane 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 ferric oxide red and 10 parts of diluent, wherein the diluent is formed by mixing dimethylbenzene and butyl acetate according to a mass ratio of 70:30; the B component is 25 parts by weight of HDI curing agent (model N3375 curing agent manufactured by Bayer company), and the C component is 3 parts by weight of ethyl silicate;
the structural formula of the polyurea resin is shown as formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 9 carbon atoms, and n has a value of 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 has a value of 3, and q has a value of 5.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to preset weight parts for standby;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is thoroughly dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 25min, then heating to 90 ℃, preserving heat for 3h, adding active bactericidal substances, stirring for 15min, stopping stirring, cooling to 50 ℃, and preserving heat for 3h to obtain modified resin;
(3) Adding the modified resin into a stirring device, adding a dispersing agent and an anti-settling agent, stirring and mixing uniformly, adding zinc oxide and pigment, stirring and mixing for 30min, adding a diluent to adjust viscosity, grinding to fineness less than 60 mu m, filtering and packaging after detection is qualified, thus obtaining the component A.
The marine long-acting antifouling paint prepared in the embodiment is subjected to performance test, and the test result is equivalent to that of the embodiment 1.
Example 3
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: 45 parts of polyurea resin, 10 parts of low molecular weight bisphenol A type epoxy resin, 15 parts of organosilane 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 ferric oxide red and 5 parts of diluent, wherein the diluent is formed by mixing dimethylbenzene and butyl acetate according to a mass ratio of 80:20; the component B is 30 parts by weight of HDI curing agent (model HT100 curing agent manufactured by Wanhua chemistry), and the component C is 5 parts by weight of ethyl silicate;
the structural formula of the polyurea resin is shown as formula I:
wherein R is 1 ，R 2 Each independently represents an alkylene group having 10 carbon atoms, and n has 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 has a value of 4, and q has a value of 6.
The component A is prepared by the following steps:
(1) Weighing the raw materials according to preset weight parts for standby;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is thoroughly dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 30min, then heating to 110 ℃, preserving heat for 1h, adding active bactericidal substances, stirring for 20min, stopping stirring, cooling to 70 ℃, and preserving heat for 1h to obtain modified resin;
(3) Adding the modified resin into a stirring device, adding a dispersing agent and an anti-settling agent, stirring and mixing uniformly, adding zinc oxide and pigment, stirring and mixing for 40min, adding a diluent to adjust viscosity, grinding to fineness less than 60 mu m, filtering and packaging after detection is qualified, thus obtaining the component A.
The marine long-acting 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 illustrative of the embodiments using the present teachings, and is not intended to limit the scope of the present teachings to any particular modification or variation of the present teachings by those skilled in the art.
Claims (3)
1. A functional marine long-acting antifouling paint is characterized in that: the composite material 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 organosilane 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 of isocyanate curing agent, the component C is 3-5 parts of ethyl silicate, and the structural formula of the polyurea resin is shown as 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 having a value in the range of 2 to 4, q is an integer having a value in the range of 3 to 6;
the active bactericidal substance is dexmedetomidine;
the component A is prepared by the following steps:
(1) Weighing the raw materials according to preset weight parts for standby;
(2) Adding epoxy resin into a reaction kettle, heating until the epoxy resin is thoroughly dissolved, then adding polyurea resin, stirring and mixing uniformly, then adding organosilane resin, stirring for 20-30 min, heating to 90-110 ℃, preserving heat for 1-3 h, then adding active bactericidal substances, stirring for 10-20 min, stopping stirring, cooling to 50-70 ℃, and preserving heat for 1-3 h to obtain modified resin;
(3) Adding the modified resin into a stirring device, adding a dispersing agent and an anti-settling agent, stirring and mixing uniformly, adding zinc oxide and pigment, stirring and mixing for 20-40 min, adding a diluent to adjust viscosity, grinding to fineness less than 60 mu m, filtering and packaging after detection is qualified, thus obtaining the component A.
2. A functional marine long-acting antifouling paint according to claim 1, wherein: the diluent is formed by mixing dimethylbenzene and butyl acetate, wherein the dimethylbenzene accounts for 60-80% by mass, and the butyl acetate accounts for 20-40% by mass.
3. A functional marine long-acting 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.
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| 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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