Coating composition of modified organic silicon transition layer, transition layer as well as preparation method and application of transition layer

Abstract

The invention discloses a coating composition of a modified organic silicon transition layer, the transition layer as well as a preparation method and application of the transition layer. The coating composition comprises a first component and a second component, wherein the first component comprises a functional polyurea modified polysiloxane prepolymer, and the second component comprises an epoxy resin prepolymer. The coating composition of the polyurea and the epoxy modified organic silicon transition layer and the modified organic silicon transition layer provided by the invention have excellent connectivity, meanwhile, the construction method of the coating composition is simple and convenient, and the coating composition has an application prospect in the field of marine antifouling engineering.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling, and in particular relates to a coating composition of a modified organic silicon transition layer, a transition layer, and a preparation method and application thereof. Background Art

[0002] The fouling of marine organisms on the surface of facilities and equipment has caused great harm to marine transportation and the exploration and development of marine resources, such as reducing the speed of ships and increasing fuel consumption. However, in the harsh marine environment, the fouling and corrosion problems of marine engineering materials and equipment have become increasingly prominent, bringing huge economic losses and safety hazards. The annual loss caused by marine corrosion in my country is about 100 billion yuan, of which about 40% is caused by biological fouling. Marine antifouling is recognized as a global problem. In the 1970s, tributyltin-based marine antifouling coatings were developed, which have good antifouling properties and construction performance. However, due to its long-term toxicity to non-target organisms and serious damage to the marine ecological environment, it has been banned worldwide since 2008. Siloxane-based (PDMS) coating materials can form low biological attachment surfaces by relying on their extremely low elastic modulus and low surface tension coefficient. This is a means of preventing biological attachment by relying on the interface interaction mechanism, and is a green and environmentally friendly marine antifouling material. However, conventional methylsiloxane coatings have the disadvantages of increasing biofouling and decreasing drag reduction effects over time. Therefore, an improved polysiloxane-based fouling control coating composition is needed.

[0003] Using other functional segments to improve antifouling performance is an important improvement method. For example, WO2007053163A2 discloses an improved siloxane-based antifouling material, whose resin includes one or more copolymers (such as block copolymers, graft copolymers, etc.) in a suitable number, and such copolymers can be grafted with one or more polymer chains (including polysiloxane) onto the polysiloxane main chain, and these grafted polymers can carry biocidal groups to provide biocidal and / or fouling release properties. WO2011076856A1, WO2013000478A1 and WO2013000477A1 disclose a polysiloxane-based fouling control coating system, which includes a biocide and one or more hydrophilic segment-modified polysiloxanes, and by combining the biocidal component in the antifouling coating with the silicon-based defouling coating to control the leaching of the biocide, the biofouling-free period of the organosilicon-based coating is extended, thereby obtaining a fouling-free, low-friction surface while using a relatively small amount of biocide. Compared with traditional silicone antifouling coatings, silicone-based antifouling coatings such as silicone hydrogel and pure silicone can maintain a fouling-free state for a longer time than conventional siloxane-based fouling release coatings. However, this type of antifouling coating can form a low biological attachment surface by relying on its low surface tension coefficient, but at the same time, this low surface energy property leads to weak adhesion to the substrate, high construction requirements, and easy peeling of the coating, which greatly limits the application of this type of coating.

[0004] At present, epoxy-based connecting paint is commonly used, and its base resin is mainly epoxy resin. Although it solves the problem of poor adhesion between connecting paint resin and epoxy antirust primer, it has a large structural difference with silicone-based antifouling topcoat resin and poor compatibility, which leads to the phenomenon of reduced adhesion during use. In CN102964516A, side chain epoxy groups are introduced into the acrylic resin structure compatible with the antifouling topcoat resin to improve the compatibility of the resin with the epoxy antirust primer resin, so as to improve the adhesion strength of the antirust and antifouling paint, but the bonding performance with silicone antifouling paint is poor and easy to peel off. At present, there are fewer types of commercialized antifouling paints (especially silicone hydrogels) on the market. The SeaLionRepulse series of silicone low surface energy antifouling paints developed by the Norwegian Jotun coating company consists of three components, and its antifouling period can reach 5-10 years. Its matching connecting paint is SeaLion Tiecoat silicone low surface energy connecting paint, which is composed of three components, component A is base material, component B is curing agent, and component C is accelerator. The operation is complicated during coating and the construction environment requirements are high. U.S. Patent No. 4996112 discloses an epoxy silicone connecting paint resin, which has improved adhesion with silicone antifouling topcoat, but has poor adaptability with other types of substrates. The connecting paint disclosed in CN106336799A is a silicone epoxy connecting paint used in conjunction with a fouling release antifouling paint. The strength of the connecting layer is high after curing, and the adhesion with the primer is good, but the connecting paint has poor adhesion with the fouling release antifouling paint, and it is easy to foam after being soaked in seawater. There are few reports on commercialized fouling release antifouling paints in the domestic market, and there are large barriers and bottlenecks, and most of them are still in the research stage. Summary of the invention

[0005] The main purpose of the present invention is to provide a coating composition of a modified organic silicon transition layer, a transition layer and a preparation method and application thereof, so as to overcome the shortcomings of the prior art.

[0006] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0007] An embodiment of the present invention provides a coating composition for a modified silicone transition layer, the coating composition comprising a first component and a second component; wherein the first component comprises a functional polyurea-modified polysiloxane prepolymer, and the second component comprises an epoxy resin prepolymer.

[0008] In some more specific embodiments, the functional polyurea-modified polysiloxane prepolymer has a structure as shown in formula (I):

[0009]

[0010] Among them, R0 is R2 is selected from C 1-6alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000, and the curve represents a macromolecular segment; R1 is selected from alkyl, aryl or alkenyl; o is selected from 1 to 100.

[0011] In some specific embodiments, the epoxy resin prepolymer has a structure as shown in formula (II):

[0012]

[0013] Wherein, R7 is selected from an organic segment, and the organic segment is derived from alkanes or aromatic hydrocarbons; and p is selected from 2 to 25.

[0014] The present invention also provides a method for preparing the aforementioned modified organic silicon transition layer coating composition, which comprises:

[0015] The functional polyurea modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler and the solvent are uniformly mixed to form a first component;

[0016] Evenly mixing epoxy resin prepolymer, butanol and solvent to form a second component;

[0017] And, the first component and the second component are mixed evenly to prepare a coating composition of a modified organic silicon transition layer.

[0018] The embodiment of the present invention further provides a modified organic silicon transition layer formed by the coating composition of the aforementioned modified organic silicon transition layer, wherein the resin in the modified organic silicon transition layer includes polyurea and epoxy-modified organic silicon resin.

[0019] The present invention also provides a method for preparing the modified organic silicon transition layer, which comprises:

[0020] The first component and the second component in the coating composition of the modified organic silicon transition layer are uniformly mixed to form a mixture, and then the mixture is applied to the surface of the substrate and reacted to obtain the modified organic silicon transition layer.

[0021] The present invention also provides a method for constructing an organosilicon-based antifouling coating on a substrate surface, which comprises:

[0022] Applying a primer composition at least once on the surface of a substrate to form a primer layer;

[0023] The first component and the second component in the aforementioned coating composition are mixed evenly, and applied to the surface of the primer layer for reaction to obtain a modified organic silicon transition layer;

[0024] Furthermore, at least one layer of organosilicon-based antifouling coating or organosilicon hydrogel-based antifouling coating is coated on the modified organosilicon transition layer.

[0025] The embodiments of the present invention also provide the use of the aforementioned coating composition or modified organic silicon transition layer in the field of antifouling engineering in a marine environment.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The technical solution of the present invention can greatly improve the surface adhesion between the substrate / primer and the silicone-based antifouling coating, and improve the workability of the silicone-based antifouling coating. The adhesion of the coating on the epoxy substrate is not less than 6MPa, the adhesion of the coating on the polyurea substrate is not less than 4MPa, the adhesion of the coating on the standard concrete substrate is not less than 3MPa, and the adhesion of the coating on the steel substrate is not less than 5MPa, which is significantly greater than the industry value. The adhesion of the silicone resin on the substrate is increased by 4 to 10 times by using the coating as a connecting paint;

[0028] (2) The coating composition of the modified silicone transition layer proposed in the present invention contains polyurea segments, epoxy resin segments and silicone segments. This composite segment structure has a wider range of applications for substrates / primers, and the segment content can be adjusted according to demand. It is suitable for most application scenarios on the market, such as metal substrates, concrete substrates, engineering resin substrates, epoxy resin primers, polyurethane resin primers, polyurea resin primers and silicone resin primers;

[0029] (3) The method for preparing the functional polyurea-modified polysiloxane prepolymer in the coating composition of the present invention has the characteristics of simple operation and low reaction temperature; the coating mixture formed by mixing the first component and the second component has high reaction activity, adjustable curing time, and the surface drying time can be controlled within 10 minutes to 2 hours; it can be cross-linked and cured at low temperature, and the cross-linking curing temperature can be as low as -10°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 is an infrared spectrum of the amino-modified polysiloxane prepolymer in Example 1 of the present invention;

[0032] Figure 2 is a nuclear magnetic resonance spectrum of the amino-modified polysiloxane prepolymer in Example 1 of the present invention;

[0033] Figure 3 is an infrared spectrum of the amino-modified polysiloxane prepolymer in Example 2 of the present invention;

[0034] Figure 4 This is a nuclear magnetic resonance spectrum of the amino-modified polysiloxane prepolymer in Example 2 of the present invention. DETAILED DESCRIPTION

[0035] In view of the defects of the prior art, the inventor of this case has proposed the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] Specifically, as one aspect of the technical solution of the present invention, a coating composition for a modified silicone transition layer includes a first component and a second component; wherein the first component includes a functional polyurea-modified polysiloxane prepolymer, and the second component includes an epoxy resin prepolymer.

[0037] In some preferred embodiments, the functional polyurea-modified polysiloxane prepolymer has a structure as shown in formula (I):

[0038]

[0039] Among them, R0 is R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000, the curve represents a macromolecular segment, such as a similar silicone segment; R1 is selected from alkyl, aryl or alkenyl; o is selected from 1 to 100.

[0040] In some preferred embodiments, the epoxy resin prepolymer has a structure as shown in formula (II):

[0041]

[0042] Wherein, R7 is selected from an organic segment, and the organic segment is derived from alkanes or aromatic hydrocarbons; and p is selected from 2 to 25.

[0043] In some preferred embodiments, the epoxy resin prepolymer includes bisphenol A epoxy resin and / or E51 epoxy resin, but is not limited thereto.

[0044] In some preferred embodiments, the method for preparing the functional polyurea-modified polysiloxane prepolymer comprises:

[0045] A first mixed reaction system comprising hydroxy silicone oil, amino silicate, silicate and a first catalyst is subjected to a decondensation reaction to obtain an amino-modified polysiloxane prepolymer;

[0046] And, the amino-modified polysiloxane prepolymer is subjected to an addition reaction with isocyanate to obtain a functional polyurea-modified polysiloxane prepolymer.

[0047] Further, the hydroxy silicone oil includes methyl hydroxy silicone oil and / or phenyl hydroxy silicone oil, but is not limited thereto.

[0048] Furthermore, the hydroxy silicone oil has a structure as shown in formula (III):

[0049]

[0050] Wherein, R5 and R6 are independently selected from alkyl, aryl or alkenyl, and n is selected from 5 to 25,000.

[0051] Further, the amino-containing silicate includes any one or more combinations of (3-aminopropyl)ethyldiethoxysilane, 4-anilinotriethoxysilane, 3-aminopropyltriethoxysilane, and N-aminoethyl-3-aminopropyltriethoxysilane, but is not limited thereto.

[0052] Furthermore, the amino-containing silicate has a structure as shown in formula (IV):

[0053]

[0054] Wherein, R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R 11 Selected from methyl, ethyl, propyl or isopropyl.

[0055] Further, the silicate includes a difunctional silicate monomer and / or a multifunctional silicate monomer; wherein the difunctional silicate monomer includes dimethoxydimethylsilane and / or diethoxydimethylsilane; the multifunctional silicate monomer includes ethyl orthosilicate and / or trimethoxymethylsilane, and is not limited thereto.

[0056] Furthermore, the silicate includes a compound having a structure as shown in any one of formulas (V)-(VI):

[0057]

[0058] wherein R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl or alkenyl; R 11 is selected from methyl, ethyl, propyl or isopropyl; x is selected from 3 or 4.

[0059] Further, the first catalyst includes dibutyltin dilaurate, but is not limited thereto.

[0060] Furthermore, the amino-modified polysiloxane prepolymer has a structure as shown in formula (VII):

[0061]

[0062] Wherein, R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000; the curve represents the macromolecular segment.

[0063] Furthermore, the isocyanate has a structure as shown in formula (VIII):

[0064]

[0065] Wherein, R1 is selected from alkyl, aryl or alkenyl.

[0066] Furthermore, the decondensation reaction of the first mixed reaction system is carried out under stirring conditions, and the stirring rate adopted is 400-1000r / min.

[0067] Furthermore, the reaction temperature of the decondensation reaction of the first mixed reaction system is 50-130°C.

[0068] Furthermore, the reaction time of the decondensation reaction of the first mixed reaction system is 2-24h.

[0069] Furthermore, in a protective atmosphere, under the condition of a stirring speed of 400-1000 r / min, isocyanate is slowly added to the amino-modified polysiloxane prepolymer at -10-50° C. to carry out an addition reaction.

[0070] Furthermore, the reaction temperature of the amino-modified polysiloxane prepolymer and isocyanate is 40-90°C.

[0071] Furthermore, the reaction time of the amino-modified polysiloxane prepolymer and isocyanate is 1-24 hours.

[0072] Furthermore, the mass ratio of the hydroxy silicone oil, the amino-containing silicate and the silicate is 100-50:60-20:30-10.

[0073] Furthermore, the mass ratio of the amino-modified polysiloxane prepolymer to the isocyanate is 100-50:40-5.

[0074] In some more specific embodiments, the method for preparing the functional polyurea-modified polysiloxane prepolymer comprises:

[0075] (1) Preparation of amino-modified polysiloxane prepolymer: hydroxy silicone oil, amino-containing silicate, silicate and the first catalyst are mixed and subjected to decondensation reaction, and small molecular substances generated by the reaction are removed to obtain amino-modified polysiloxane prepolymer. The chemical reaction process is shown in the following formula:

[0076]

[0077] (2) Preparation of polyurea-modified polysiloxane prepolymer: slowly adding isocyanate monomer to amino-modified polysiloxane prepolymer, and the amine and isocyanate undergo addition reaction to obtain polyurea-modified polysiloxane prepolymer. The chemical reaction process is shown in the following formula;

[0078]

[0079] Furthermore, the decondensation reaction temperature in step (1) is 50-130° C., and the reaction time is 2-24 h.

[0080] Furthermore, in the step (1), the mass ratio of hydroxy silicone oil, amino silicate and silicate is 100-50:60-20:30-10.

[0081] Furthermore, in the step (2), the temperature when adding the raw materials is -10-50°C. After the raw materials are added, the reaction temperature is adjusted to 40-90°C, and the reaction time is 1-24h.

[0082] Furthermore, in the step (2), the mass ratio of the amino-modified polysiloxane prepolymer to the isocyanate monomer is 100-50:40-5.

[0083] Further, in the preparation of the polyurea-modified polysiloxane prepolymer, an appropriate amount of catalyst can be added in stage (1) and / or stage (2), and the effect achieved is to accelerate the reaction process. Suitable catalysts include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin dioctanoate, tin naphthenate, tin butyrate, tin oleate, bismuth 2-ethylhexanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt naphthenate and titanium naphthenate, tetrabutyl titanate, triethanolamine titanate, titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, etc. The catalyst can be used alone or in combination of two or more catalysts. In some preferred embodiments, the first component also includes a wetting dispersant, an anti-settling agent, a pigment filler, and a solvent.

[0084] In some preferred embodiments, the second component further comprises butanol and a solvent.

[0085] Furthermore, the first component includes the following components calculated in parts by weight: 25-60 parts of functional polyurea-modified polysiloxane prepolymer, 0.5-2 parts of wetting and dispersing agent, 0.5-3 parts of anti-settling agent, 12-40 parts of pigments and fillers, and 5-50 parts of solvents.

[0086] Furthermore, the second component includes the following components calculated in parts by weight: 70-95 parts of epoxy resin prepolymer, 0-15 parts of butanol, and 5-30 parts of solvent.

[0087] Furthermore, the mass ratio of the first component to the second component is 15-1:1.

[0088] Furthermore, the NDJ-4 rotational viscosity of the first component is 1.0-6.0 Pa.S.

[0089] Furthermore, the NDJ-4 rotational viscosity of the first component is 1.5-3.5 Pa.S.

[0090] Furthermore, the coating-4 cup viscosity of the second component is 30-120s.

[0091] Furthermore, the coating-4 cup viscosity of the second component is 30-60s.

[0092] Furthermore, the anti-settling agent includes any one or more combinations of fumed silica, organic bentonite, and polyamide wax powder, but is not limited thereto.

[0093] Furthermore, the pigments and fillers include any one or more combinations of titanium dioxide, red iron oxide, carbon black, barium sulfate, mica powder, talc powder, and silica powder, but are not limited thereto.

[0094] Further, the wetting and dispersing agent includes ANTI-TERRA-U, Disponer923S, RG-5172, DISPERBYK-110, γ-aminopropyltriethoxysilane, glyceryl stearate, etc., but is not limited thereto.

[0095] Further, the solvent includes xylene and / or butanol, but is not limited thereto.

[0096] The first component and the second component of the present invention may contain an appropriate amount of solvent, which usually accounts for 5-50% of the volume ratio of the coating composition, including ethanol, cyclohexane, toluene, xylene and naphtha solvents, methoxypropyl acetate, n-butyl acetate, 2-ethoxyethyl acetate and mixtures thereof, or the solvent system may include water or a water base.

[0097] In order to improve the mechanical properties, durability and aesthetics of the coating, the first component and / or the second component used to form the coating composition may include pigments and fillers, such as red iron oxide, silicon dioxide, titanium dioxide, zinc oxide, carbon black, graphite, zinc sulfide, antimony oxide, sodium aluminosilicate, phthalocyanine blue, phthalocyanine green, aluminum cobalt oxide, quinocetone yellow, calcium carbonate, calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, silica, magnesium oxide and quartz powder, etc. Fillers (and pigments) can also be added in the form of nanoparticles and nanofibers.

[0098] In addition, the first component and the second component used to form the coating composition may further contain additives such as surfactants, thickeners, anti-settling agents, antioxidants, etc., accounting for 0 to 10 wt % of the dry weight of the coating composition.

[0099] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned modified organic silicon transition layer coating composition, which comprises:

[0100] The functional polyurea modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler and the solvent are uniformly mixed to form a first component;

[0101] Evenly mixing epoxy resin prepolymer, butanol and solvent to form a second component;

[0102] And, the first component and the second component are mixed evenly to prepare a coating composition of a modified organic silicon transition layer.

[0103] Another aspect of the embodiments of the present invention further provides a modified silicone transition layer formed by the aforementioned modified silicone transition layer coating composition, wherein the resin in the modified silicone transition layer includes polyurea and epoxy-modified silicone resin.

[0104] In some preferred embodiments, the polyurea and epoxy-modified silicone resin has a structure as shown in Formula (IX):

[0105]

[0106] Among them, R0 is R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000; R1 is selected from alkyl, aryl or alkenyl; R7 is selected from an organic segment, and the organic segment is derived from alkanes or aromatics; o is selected from 1 to 100; the curve represents the macromolecular segment.

[0107] Furthermore, the first component and the second component are mixed to prepare polyurea and epoxy-modified silicone resin: the polyurea-modified polysiloxane prepolymer in the first component and the epoxy resin prepolymer in the second component are mixed, and the first component and the second component are mixed to carry out epoxy ring-opening addition reaction, and after the reaction is completed, polyurea and epoxy-modified silicone resin are obtained. The chemical reaction process of polyurea and epoxy-modified silicone resin is shown in the following formula:

[0108]

[0109] Furthermore, the mass ratio of the polyurea modified polysiloxane prepolymer to the epoxy resin prepolymer is 100-50:50-5.

[0110] Further, the epoxy resin prepolymer in the second component includes bisphenol A epoxy resin, but is not limited thereto.

[0111] Further, the epoxy resin prepolymer in the second component includes E51 epoxy resin, but is not limited thereto.

[0112] Furthermore, in the coating resin system, the organosilicon accounts for 20-60 wt % of the resin system, the epoxy resin accounts for 10-60 wt % of the resin system, and the polyurea monomer segment accounts for 5-30 wt % of the resin system.

[0113] In some preferred embodiments, the content of the silicone segment in the polyurea and epoxy modified silicone resin is 20 to 60 wt %.

[0114] In some preferred embodiments, the content of epoxy resin segments in the polyurea and epoxy-modified silicone resin is 10 to 60 wt %.

[0115] In some preferred embodiments, the content of the polyurea monomer segment in the polyurea and epoxy-modified silicone resin is 5 to 30 wt %.

[0116] In some preferred embodiments, the mass ratio of the polyurea and epoxy-modified silicone resin to the coating composition is 20 to 90:100.

[0117] Furthermore, the mass ratio of the polyurea and epoxy-modified silicone resin to the coating composition is 30 to 80:100.

[0118] Another aspect of the embodiments of the present invention further provides a method for preparing the aforementioned modified organic silicon transition layer, which comprises:

[0119] The first component and the second component in the coating composition of the modified organic silicon transition layer are uniformly mixed to form a mixture, and then the mixture is applied to the surface of the substrate and reacted to obtain the modified organic silicon transition layer.

[0120] In some preferred embodiments, the NDJ-4 rotational viscosity of the mixture is 0.5-5.5 Pa.S, and the solid content of the mixture is above 55 wt%.

[0121] In some preferred embodiments, the ambient temperature (construction temperature) when the mixture is applied to the substrate surface for reaction is -10-50°C.

[0122] In some preferred embodiments, the reaction time when the mixture is applied to the surface of the substrate is 15 minutes to 24 hours.

[0123] In some preferred embodiments, the substrate includes metal steel plate (Q235 steel plate, ≥10.0 MPa), concrete (≥5.0 MPa), epoxy composite board (≥8.0 MPa), silicone composite board (≤1.0 MPa), and is not limited thereto.

[0124] Another aspect of the embodiments of the present invention further provides a method for constructing an organosilicon-based antifouling coating on a substrate surface, comprising:

[0125] Applying a primer composition at least once on the surface of a substrate to form a primer layer;

[0126] The first component and the second component in the aforementioned coating composition are mixed evenly, and applied to the surface of the primer layer for reaction to obtain a modified organic silicon transition layer;

[0127] Furthermore, at least one layer of organosilicon-based antifouling coating or organosilicon hydrogel-based antifouling coating is coated on the modified organosilicon transition layer.

[0128] In some preferred embodiments, the primer composition includes any one or more combinations of an epoxy-based primer composition, a polyurethane / polyurea-based primer composition, and a silicone-based primer composition, but is not limited thereto.

[0129] In some preferred embodiments, the mixture of the first component and the second component is coated on the surface of the tie layer 1-4 times by coating; wherein the dry film thickness of a single coat is above 100 μm.

[0130] In some preferred embodiments, the substrate includes metal steel plate (Q235 steel plate, ≥10.0 MPa), concrete (≥5.0 MPa), epoxy composite board (≥8.0 MPa), silicone composite board (≤1.0 MPa), and is not limited thereto.

[0131] In some preferred embodiments, the silicone-based antifouling coating, silicone hydrogel-based antifouling coating, can specifically be Hempaguard series developed by Hempel, SeaLion Repulse series developed by Jotun Coatings, and the like.

[0132] The coating composition of polyurea and epoxy-modified organic silicon transition layer and the modified organic silicon transition layer provided by the present invention have excellent connectivity, and the coating composition has a simple construction method and has application prospects in the field of marine antifouling engineering.

[0133] The present invention proposes a coating composition of a modified organic silicon transition layer, a transition layer, and a preparation method and application thereof. The present invention innovatively solves the above-mentioned bottleneck problems faced by organic silicon antifouling coatings in coating engineering through reasonable molecular structure design, combined with the principle of similar compatibility and hydrogen bonding. The basic principle is to modify the organic silicon resin coating by using polyurea segments and epoxy resin segments, and further prepare a connecting paint between the organic silicon-based antifouling resin and the substrate / anticorrosive coating. The polyurea segments and epoxy resin segments contain a large number of polar functional groups such as hydroxyl, carbonyl, and amino groups, which can effectively combine with the metal substrate or anticorrosive coating, improve the bonding force between the connecting paint and the substrate, and also improve the mechanical strength and toughness of the coating itself. On the other hand, the connecting paint contains a large number of organic silicon segments, and the organic silicon segments float on the surface of the coating by themselves during the curing and cross-linking stage. Based on the principle of similar compatibility, the connecting paint coating can be effectively connected with the organic silicon antifouling coating, improve the bonding force between the organic silicon antifouling coating and the substrate, and reduce the construction difficulty of the organic silicon antifouling coating. In addition, the preparation method adopted by the present invention has the characteristics of simple operation and low reaction temperature, and the prepared polyurea epoxy modified silicone connecting paint has the advantage of a wide range of applications.

[0134] Another aspect of the embodiments of the present invention further provides the use of the aforementioned modified organic silicon transition layer coating composition or the modified organic silicon transition layer in the field of antifouling engineering in a marine environment.

[0135] For example, it can be used as a connecting paint on the surfaces of ships, fishing boats, cruise ships, docks, submersibles, fishing nets, etc.

[0136] Technical description:

[0137] Note 1: When preparing amino-terminated polysiloxane prepolymer, adding trimethoxymethylsilane, tetraethoxysilane and other appropriate multifunctional siloxane monomers to carry out decondensation reaction can obtain amino-terminated polysiloxane prepolymer with dendritic structure or micro-crosslinked network structure, the purpose of which is to improve the mechanical strength of the subsequent transition coating. However, in this process, the amount of multifunctional monomers and the progress of the reaction should be controlled. Too high a multifunctional monomer and a high reaction progress will cause gelation, resulting in reaction failure.

[0138] Note 2: In the process of preparing polyurea-modified polysiloxane prepolymer, the reaction temperature should be appropriately lowered and the isocyanate should be dripped into the reactor. The reason for adopting this method is that the process of amino and isocyanate generating urea groups is an exothermic reaction, accompanied by the generation of a large amount of heat. Local high temperature is likely to produce a large amount of by-products and polyurea-modified polysiloxane prepolymers with excessively high molecular weights, which affect the performance of the connecting coating. The method of lowering the reaction temperature and dripping the raw materials can ensure that the reaction proceeds evenly and improve the reaction yield.

[0139] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0140] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0141] Example 1 (Micro-crosslinked amino-modified polysiloxane prepolymer)

[0142] Preparation of polyurea modified polysiloxane prepolymer

[0143] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 50 parts of hydroxy silicone oil with a molecular weight of about 750, 40 parts of (3-aminopropyl) ethyldiethoxysilane, 10 parts of trimethoxymethylsilane and 2 to 3 drops of dibutyltin dilaurate are fully mixed and added to a 1000 ml reaction bottle. The temperature is raised to 110°C at a speed of 600 r / min and the stirring reaction is continued for 8 hours. During the reaction, the small molecular substances generated by the reaction are separated from the reaction bottle by vacuum evaporation. As the reaction proceeds, the viscosity of the reactants gradually increases. After the reaction is completed, the temperature is lowered to room temperature to obtain an amino-modified polysiloxane prepolymer, wherein the infrared spectrum of the amino-modified polysiloxane prepolymer is shown in the figure Figure 1 The NMR spectrum is shown in Figure 2 shown.

[0144] (2) Preparation of polyurea-modified polysiloxane prepolymer: Add 100 parts of amino-modified polysiloxane prepolymer and 50 parts of toluene to a reaction bottle, stir at 600 r / min, and introduce nitrogen. Slowly drip 10 parts of isophorone diisocyanate into the reaction bottle at room temperature, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 60°C and react for 12 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyurea-modified polysiloxane prepolymer, which is then left to stand for use.

[0145] Example 2 (Silicon segment molecular weight reduction, micro-crosslinked amino-modified polysiloxane prepolymer)

[0146] Preparation of polyurea modified polysiloxane prepolymer

[0147] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, thoroughly mix 60 parts of hydroxy silicone oil with a molecular weight of about 500, 40 parts of (3-aminopropyl)ethyldiethoxysilane, 10 parts of trimethoxymethylsilane and 2 to 3 drops of dibutyltin dilaurate, add to a 1000 ml reaction bottle, heat to 100°C at a speed of 1000 r / min, and continue stirring to react for 12 hours. The small molecular substances generated during the reaction are separated from the reaction bottle by vacuum evaporation. As the reaction proceeds, the viscosity of the reactants gradually increases. After the reaction is completed, the temperature is lowered to room temperature to obtain an amino-modified polysiloxane prepolymer, wherein the infrared spectrum of the amino-modified polysiloxane prepolymer is as shown in the figure. Figure 3 The NMR spectrum is shown in Figure 4 shown.

[0148] (2) Preparation of polyurea-modified polysiloxane prepolymer: Add 110 parts of amino-modified polysiloxane prepolymer and 40 parts of toluene to a reaction bottle, stir at 1000 r / min, and introduce nitrogen. Slowly drip 15 parts of isophorone diisocyanate into the reaction bottle at room temperature, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 80°C and react for 8 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyurea-modified polysiloxane prepolymer, which is then left to stand for use.

[0149] Example 3 (Comb-shaped amino-modified polysiloxane prepolymer, slightly cross-linked polyurea-modified polysiloxane prepolymer)

[0150] Preparation of polyurea modified polysiloxane prepolymer

[0151] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 60 parts of hydroxy silicone oil with a molecular weight of about 500, 40 parts of (3-aminopropyl) ethyl diethoxysilane, and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle. The temperature was raised to 120°C at a speed of 500 r / min, and the stirring reaction was continued for 6 hours. The small molecular substances generated during the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0152] (2) Preparation of polyurea-modified polysiloxane prepolymer: Add 100 parts of amino-modified polysiloxane prepolymer to a reaction bottle, stir at 500 r / min, and introduce nitrogen. Slowly drip 15 parts of isophorone diisocyanate into the reaction bottle at room temperature, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 70°C and react for 18 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyurea-modified polysiloxane prepolymer, which is then left to stand for use.

[0153] Example 4 (Aminosilane is the cross-linking point of the organosilicon chain segment)

[0154] Preparation of polyurea modified polysiloxane prepolymer

[0155] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 100 parts of hydroxy silicone oil with a molecular weight of about 750, 50 parts of 3-aminopropyltriethoxysilane, 10 parts of diethoxydimethylsilane and 2 to 3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 90°C at 800 r / min, and stirred for 16 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, the temperature was lowered to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0156] (2) Preparation of polyurea-modified polysiloxane prepolymer: Add 150 parts of amino-modified polysiloxane prepolymer and 50 parts of toluene into a reaction bottle, stir at 800 r / min, and introduce nitrogen. Slowly drop 10 parts of xylene diisocyanate into the reaction bottle at room temperature, always paying attention to the changes in the reaction solution to avoid gelation. After the addition is complete, heat to 50°C and react for 24 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyurea-modified polysiloxane prepolymer, which is then left to stand for use.

[0157] Example 5 (Linear amino-modified polysiloxane prepolymer and polyurea-modified polysiloxane prepolymer)

[0158] Preparation of polyurea modified polysiloxane prepolymer

[0159] (1) Preparation of amino-modified polysiloxane prepolymer: At room temperature, 50 parts of hydroxy silicone oil with a molecular weight of about 2000, 50 parts of 3-aminopropyldimethylethoxysilane and 2-3 drops of dibutyltin dilaurate were fully mixed and added to a 1000 ml reaction bottle, heated to 80°C at 400 r / min, and stirred for 24 hours. During the reaction, the small molecular substances generated by the reaction were separated from the reaction bottle by vacuum evaporation. As the reaction proceeded, the viscosity of the reactants gradually increased. After the reaction was completed, it was cooled to room temperature to obtain an amino-modified polysiloxane prepolymer.

[0160] (2) Preparation of polyurea-modified polysiloxane prepolymer: Add 100 parts of amino-modified polysiloxane prepolymer and 50 parts of xylene to a reaction bottle, stir at 400 r / min, and introduce nitrogen. Slowly drip 20 parts of xylene diisocyanate into the reaction bottle at room temperature, always paying attention to the changes in the reaction solution to avoid rapid temperature rise and gelation. After the addition is complete, heat to 85°C and react for 24 hours. After the reaction is completed, cool to room temperature to obtain a viscous polyurea-modified polysiloxane prepolymer, which is then left to stand for use.

[0161] Example 6 (using the polyurea-modified polysiloxane prepolymer in Example 1)

[0162] Preparation of polyurea and epoxy modified silicone transition layer coating composition

[0163] In this embodiment, the polyurea and epoxy modified silicone transition layer coating comprises a first component and a second component, wherein the first component comprises a polyurea modified silicone prepolymer and the second component comprises an epoxy resin prepolymer. Each component is made of the following ingredients based on a total weight of 100 parts:

[0164] Preparation of the first component polyurea modified polysiloxane prepolymer resin: 40 parts of the polyurea modified polysiloxane prepolymer obtained in Example 1 and 30 parts of xylene are added to a mixing pot and stirred at a speed of 3000r / min for 5 minutes, and then 0.5 parts of ANTI-TERRA-U wetting and dispersing agent and 0.5 parts of fumed silica anti-settling agent are added in sequence, and then 10 parts of red iron oxide, 10 parts of silicon micropowder, 4 parts of mica powder and 5 parts of zinc oxide are added, and stirring is continued at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 1.5Pa.S with xylene. Filter and package to obtain the first component.

[0165] Preparation of the first component epoxy resin: 90 parts of epoxy resin (E51), 5 parts of butanol and 5 parts of xylene were added into a mixing pot, dispersed at 3000 r / min for 10 minutes under a stirrer, and the viscosity of the obtained mixture was adjusted to 70S in a T-4 cup with xylene, and filtered and packaged to obtain the second component;

[0166] The first component and the second component are mixed and stirred evenly in a mass ratio of 4:1, and coated on the surface of the substrate to form a film to obtain the polyurea and epoxy-modified silicone transition layer coating.

[0167] Example 7 (using the polyurea-modified polysiloxane prepolymer in Example 2)

[0168] Preparation of polyurea and epoxy modified silicone transition layer coating composition

[0169] In this embodiment, the polyurea and epoxy modified silicone transition layer coating comprises a first component and a second component, wherein the first component comprises a polyurea modified silicone prepolymer and the second component comprises an epoxy resin prepolymer. Each component is made of the following ingredients based on a total weight of 100 parts:

[0170] Preparation of the first component polyurea modified polysiloxane prepolymer resin: 35 parts of the polyurea modified polysiloxane prepolymer obtained in Example 2 and 30 parts of xylene are added to a mixing pot and stirred at a speed of 4000r / min for 5 minutes, and then 1 part of Disponer923S wetting and dispersing agent, 1 part of polyamide wax powder anti-settling agent, and 0.5 part of fumed silica anti-settling agent are added in sequence, and then 12.5 parts of red iron oxide, 10 parts of silicon micropowder, 5 parts of mica powder, and 5 parts of zinc oxide are added, and stirring is continued at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to an NDJ-4 rotational viscosity of 2.5Pa.S with xylene. Filter and package to obtain the first component.

[0171] Preparation of the first component epoxy resin prepolymer: 85 parts of epoxy resin (E44), 5 parts of butanol and 10 parts of xylene were added into a mixing pot, dispersed at 4000 r / min for 10 minutes under a stirrer, the viscosity of the obtained mixture was adjusted to 55S in a T-4 cup with xylene, and filtered and packaged to obtain the second component;

[0172] The first component and the second component are mixed and stirred evenly in a mass ratio of 6:1, and coated on the surface of the substrate to form a film to obtain the polyurea and epoxy-modified silicone transition layer coating.

[0173] Example 8 (using the polyurea-modified polysiloxane prepolymer in Example 3)

[0174] Preparation of polyurea and epoxy modified silicone transition layer coating composition

[0175] In this embodiment, the polyurea and epoxy modified silicone transition layer coating comprises a first component and a second component, wherein the first component comprises a polyurea modified silicone prepolymer and the second component comprises an epoxy resin prepolymer. Each component is made of the following ingredients based on a total weight of 100 parts:

[0176] Preparation of the first component polyurea modified polysiloxane prepolymer resin: 50 parts of the polyurea modified polysiloxane prepolymer obtained in Example 3 and 20 parts of xylene are added to a mixing pot and stirred at a speed of 2000r / min for 5 minutes, and then 2 parts of RG-5172 wetting and dispersing agent, 3 parts of bentonite, and 1 part of fumed silica anti-settling agent are added in sequence, and then 10 parts of red iron oxide, 5 parts of mica powder, 5 parts of zinc oxide, and 4 parts of titanium dioxide are added, and stirring is continued at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to NDJ-4 rotational viscosity of 2.0Pa.S with xylene. Filter and package to obtain the first component.

[0177] Preparation of the first component epoxy resin prepolymer: 80 parts of epoxy resin (E68), 10 parts of butanol and 10 parts of xylene were added into a mixing pot, dispersed at 2000 r / min for 10 minutes under a stirrer, the viscosity of the obtained mixture was adjusted to 40S in a T-4 cup with xylene, and filtered and packaged to obtain the second component;

[0178] The first component and the second component are mixed and stirred evenly in a mass ratio of 8:1, and coated on the surface of the substrate to form a film to obtain the polyurea and epoxy-modified silicone transition layer coating.

[0179] Example 9 (using the polyurea-modified polysiloxane prepolymer in Example 4)

[0180] Preparation of polyurea and epoxy modified silicone transition layer coating composition

[0181] In this embodiment, the polyurea and epoxy modified silicone transition layer coating comprises a first component and a second component, wherein the first component comprises a polyurea modified silicone prepolymer and the second component comprises an epoxy resin prepolymer. Each component is made of the following ingredients based on a total weight of 100 parts:

[0182] Preparation of the first component polyurea modified polysiloxane prepolymer resin: 30 parts of the polyurea modified polysiloxane prepolymer obtained in Example 4 and 35 parts of xylene are added to a mixing pot and stirred at a speed of 5000r / min for 5 minutes, and then 1 part of DISPERBYK-110 wetting and dispersing agent, 2.5 parts of bentonite, and 0.5 parts of fumed silica anti-settling agent are added in sequence, and then 6 parts of zinc oxide, 5 parts of titanium dioxide, 10 parts of carbon black, 5 parts of barium sulfate, and 5 parts of talc are added and stirred at the same speed for 20 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, the viscosity is adjusted to an NDJ-4 rotational viscosity of 3.5Pa.S with xylene, and the first component is obtained by filtering and packaging.

[0183] Preparation of the first component epoxy resin prepolymer: 85 parts of epoxy resin (F-51), 5 parts of butanol and 10 parts of xylene were added into a mixing pot, dispersed at 5000r / min for 5 minutes under a stirrer, and the viscosity of the obtained mixture was adjusted to 60S in a T-4 cup with xylene, and filtered and packaged to obtain the second component;

[0184] The first component and the second component are mixed and stirred evenly in a mass ratio of 5.5:1, and coated on the surface of the substrate to form a film to obtain the polyurea and epoxy-modified silicone transition layer coating.

[0185] Example 10 (using the polyurea-modified polysiloxane prepolymer in Example 5)

[0186] Preparation of polyurea and epoxy modified silicone transition layer coating composition

[0187] In this embodiment, the polyurea and epoxy modified silicone transition layer coating comprises a first component and a second component, wherein the first component comprises a polyurea modified silicone prepolymer and the second component comprises an epoxy resin prepolymer. Each component is made of the following ingredients based on a total weight of 100 parts:

[0188] Preparation of the first component polyurea modified polysiloxane prepolymer resin: 55 parts of the polyurea modified polysiloxane prepolymer obtained in Example 4 and 20 parts of xylene are added to a mixing pot and stirred at a speed of 6000r / min for 5 minutes, and then 1 part of Disponer904S wetting and dispersing agent, 2.5 parts of bentonite, and 1.5 parts of fumed silica anti-settling agent are added in sequence, and then 6 parts of zinc oxide, 5 parts of titanium dioxide, 4 parts of barium sulfate, and 5 parts of talcum powder are added and stirred at the same speed for 15 minutes. The mixture is ground with a sand mill to a fineness of ≤60μm, and the viscosity is adjusted to an NDJ-4 rotational viscosity of 1.5Pa.S with xylene. Filter and package to obtain the first component.

[0189] Preparation of the first component epoxy resin prepolymer: 85 parts of epoxy resin (E-51), 5 parts of butanol, and 10 parts of xylene are added into a mixing pot, dispersed at 6000r / min for 5 minutes under a stirrer, and the viscosity of the obtained mixture is adjusted to 50S in a T-4 cup with xylene, and filtered and packaged to obtain the second component;

[0190] The first component and the second component are mixed and stirred evenly in a mass ratio of 7:1, and coated on the surface of the substrate to form a film to obtain the polyurea and epoxy-modified silicone transition layer coating.

[0191] Comparative Example 1 (without epoxy segment)

[0192] Polyurea modified silicone transition layer coating composition and coating

[0193] In this comparative example 1, amino-modified polysiloxane prepolymer is prepared by the same formula and preparation method as in Example 1; the first component is prepared by the same method as in Example 6, except that the polyurea-modified organosilicon prepolymer in the first component is replaced by amino-modified polysiloxane prepolymer; the second component is prepared by the same method as in Example 6, except that the epoxy resin (E51) is replaced by isophorone diisocyanate; the polyurea-modified organosilicon transition layer coating composition and coating are prepared by the same method as in Example 6, except that the ratio of the first component to the second component is 10:1. Considering the rapid reaction between isocyanate and amino group, the coating method adopts a two-component spraying method.

[0194] Comparative Example 2 (without polyurea segment)

[0195] Epoxy modified silicone transition layer coating composition and coating

[0196] In this comparative example 1, an amino-modified polysiloxane prepolymer is prepared by the same formula parts and preparation method as in Example 2; the first component is prepared by the same method as in Example 7, except that the polyurea-modified silicone prepolymer in the first component is replaced with an amino-modified polysiloxane prepolymer; the second component is prepared by the same method as in Example 7; and the epoxy-modified silicone transition layer coating composition and coating are prepared by the same method as in Example 6, except that the dosage ratio of the first component to the second component is 4:1.

[0197] Comparative Example 3 (pure epoxy resin)

[0198] Epoxy resin transition layer coating composition and coating

[0199] In this comparative example 3, the first component is prepared by the same method as in Example 8, except that the polyurea-modified silicone prepolymer in the first component is replaced with epoxy resin E51; the second component is prepared by the same method as in Example 8, except that the epoxy resin (E68) is replaced with epoxy curing agent (T403); the epoxy resin transition layer coating composition and coating are prepared by the same method as in Example 8, except that the dosage ratio of the first component to the second component is 4:1.

[0200] Comparative Example 4 (pure silicone resin)

[0201] Silicone resin transition layer coating composition and coating

[0202] In this comparative example 4, the first component is prepared by the same method as in Example 9, except that the polyurea modified silicone prepolymer in the first component is replaced with Dow Corning 184 silicone resin prepolymer; the second component is prepared by the same method as in Example 9, except that the epoxy resin (F-51) is replaced with Dow Corning 184 silicone resin crosslinker; the silicone resin transition layer coating composition and coating are prepared by the same method as in Example 9, except that the dosage ratio of the first component to the second component is 15.5:1.

[0203] Test experiment:

[0204] The corresponding test substrates were selected according to the test items. Q235 steel plates were used for drying time and salt spray resistance. Concrete, Q235 steel plates, epoxy composite boards, silicone composite boards, comparative example 3 coatings, and comparative example 4 coatings were used as test pieces for adhesion (pull-off method) test. Each sample was coated once. The test was conducted by air spraying, and the dry film thickness was controlled at (100±10)μm. The concrete specimens were designed according to the durability standard of concrete structures, and the strength grade of concrete was C45. The test results are shown in Table 1:

[0205] Table 1 Performance test results of coatings of Examples 6-10 and Comparative Examples 1-4

[0206]

[0207] By comparing Examples 6-10 with Comparative Examples 1-4, it can be seen that the selection of epoxy segments, silicone segments and polyurea segments and their contents in the connecting paint coating (polyurea and epoxy-modified silicone transition layer coating resin) plays a very critical role in the adhesion, wetting and flexibility of the product. The selection and ratio of multifunctional monomers, cross-linking agents and prepolymers determine the cross-linking density, curing time and anti-corrosion performance of the coating.

[0208] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0209] It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the scope of protection of the purpose of the present invention and the claims shall fall within the protection scope of the present invention.

Claims

1. A coating composition for a modified organic silicon transition layer, characterized in that: The coating composition comprises a first component and a second component; wherein the first component comprises a functional polyurea-modified polysiloxane prepolymer, and the second component comprises an epoxy resin prepolymer.

2. The coating composition according to claim 1, characterized in that: The functional polyurea-modified polysiloxane prepolymer has a structure as shown in formula (I): Among them, R0 is R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000, and the curve represents a macromolecular segment; R1 is selected from alkyl, aryl or alkenyl; o is selected from 1 to 100; And / or, the epoxy resin prepolymer has a structure as shown in formula (II): Wherein, R7 is selected from an organic segment, and the organic segment is derived from alkanes or aromatic hydrocarbons; p is selected from 2 to 25; And / or, the epoxy resin prepolymer includes bisphenol A epoxy resin and / or E51 epoxy resin.

3. The coating composition according to claim 1, characterized in that The preparation method of the functional polyurea-modified polysiloxane prepolymer comprises: A first mixed reaction system comprising hydroxy silicone oil, amino silicate, silicate and a first catalyst is subjected to a decondensation reaction to obtain an amino-modified polysiloxane prepolymer; And, the amino-modified polysiloxane prepolymer is subjected to a decondensation reaction with isocyanate to obtain a functional polyurea-modified polysiloxane prepolymer.

4. The coating composition according to claim 3, characterized in that The hydroxy silicone oil includes methyl hydroxy silicone oil and / or phenyl hydroxy silicone oil; And / or, the hydroxy silicone oil has a structure as shown in formula (III): Wherein, R5 and R6 are independently selected from alkyl, aryl or alkenyl, and n is selected from 5 to 25000; And / or, the amino-containing silicate comprises any one or more combinations of (3-aminopropyl)ethyldiethoxysilane, 4-anilinotriethoxysilane, 3-aminopropyltriethoxysilane, and N-aminoethyl-3-aminopropyltriethoxysilane; And / or, the amino-containing silicate has a structure as shown in formula (IV): Wherein, R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R 11 is selected from methyl, ethyl, propyl or isopropyl; And / or, the silicate includes a difunctional silicate monomer and / or a multifunctional silicate monomer; wherein the difunctional silicate monomer includes dimethoxydimethylsilane and / or diethoxydimethylsilane; the multifunctional silicate monomer includes ethyl orthosilicate and / or trimethoxymethylsilane; And / or, the silicate comprises a compound having a structure as shown in any one of formulas (V)-(VI): wherein R3 is selected from methyl, phenyl or alkoxy; R4 is selected from alkyl, aryl or alkenyl; R 11 is selected from methyl, ethyl, propyl or isopropyl; x is selected from 3 or 4; and / or, the first catalyst comprises dibutyltin dilaurate; And / or, the amino-modified polysiloxane prepolymer has a structure as shown in formula (VII): Wherein, R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, and n is selected from 5 to 25000; And / or, the isocyanate has a structure as shown in formula (VIII): Wherein, R1 is selected from alkyl, aryl or alkenyl.

5. The coating composition according to claim 3, characterized in that The decondensation reaction of the first mixed reaction system is carried out under stirring conditions, and the stirring rate adopted is 400-1000r / min; and / or, the reaction temperature of the decondensation reaction of the first mixed reaction system is 50-130° C.; and / or, the reaction time of the decondensation reaction of the first mixed reaction system is 2-24 h; and / or, in a protective atmosphere, slowly adding isocyanate to the amino-modified polysiloxane prepolymer at -10-50° C. with a stirring speed of 400-1000 r / min for addition reaction; and / or, the reaction temperature of the amino-modified polysiloxane prepolymer and isocyanate is 40-90° C.; and / or, the reaction time of the amino-modified polysiloxane prepolymer and isocyanate is 1-24 h; and / or, the mass ratio of the hydroxy silicone oil, the amino-containing silicate and the silicate is 100-50:60-20:30-10; And / or, the mass ratio of the amino-modified polysiloxane prepolymer to the isocyanate is 100-50:40-5.

6. The coating composition according to claim 1, characterized in that: The first component also includes a wetting and dispersing agent, an anti-settling agent, a pigment and filler, and a solvent; And / or, the second component further comprises butanol and a solvent.

7. The coating composition according to claim 6, characterized in that The first component includes the following components calculated by weight: 25-60 parts of functional polyurea modified polysiloxane prepolymer, 0.5-2 parts of wetting and dispersing agent, 0.5-3 parts of anti-settling agent, 12-40 parts of pigments and fillers, and 5-50 parts of solvents; And / or, the second component comprises the following components calculated in parts by weight: 70-95 parts of epoxy resin prepolymer, 0-15 parts of butanol, and 5-30 parts of solvent; and / or, the mass ratio of the first component to the second component is 15-1:1; and / or, the NDJ-4 rotational viscosity of the first component is 1.0-6.0 Pa.S, preferably 1.5-3.5 Pa.S; and / or, the coating-4 cup viscosity of the second component is 30-120s, preferably 30-60s; And / or, the anti-settling agent includes any one or more combinations of fumed silica, organic bentonite, and polyamide wax powder; And / or, the pigments and fillers include any one or more combinations of titanium dioxide, red iron oxide, carbon black, barium sulfate, mica powder, talc powder, and silica powder; And / or, the solvent comprises xylene and / or butanol.

8. The method for preparing the coating composition of the modified organic silicon transition layer according to any one of claims 1 to 7, characterized in that: include: The functional polyurea modified polysiloxane prepolymer, the wetting and dispersing agent, the anti-settling agent, the pigment and filler and the solvent are uniformly mixed to form a first component; Evenly mixing epoxy resin prepolymer, butanol and solvent to form a second component; And, the first component and the second component are mixed evenly to prepare a coating composition of a modified organic silicon transition layer.

9. A modified organic silicon transition layer formed by the coating composition for the modified organic silicon transition layer according to any one of claims 1 to 7, characterized in that: The resin in the modified organic silicon transition layer includes polyurea and epoxy modified organic silicon resin.

10. The modified organic silicon transition layer according to claim 9, characterized in that: The polyurea and epoxy-modified silicone resin has a structure as shown in formula (IX): Among them, R0 is R2 is selected from C 1-6 alkyl or hydrogen, R3 is selected from methyl, phenyl or alkoxy, R4, R5, R6 are independently selected from alkyl, aryl or alkenyl, m is selected from 0 to 250, n is selected from 5 to 25000; R1 is selected from alkyl, aryl or alkenyl; R7 is selected from an organic segment, the organic segment is derived from alkanes or aromatics; o is selected from 1 to 100; and / or, the content of the organosilicon segment in the polyurea and epoxy-modified organosilicon resin is 20 to 60 wt %; and / or, the content of epoxy resin segments in the polyurea and epoxy-modified silicone resin is 10 to 60 wt %; and / or, the content of the polyurea monomer segment in the polyurea and epoxy-modified silicone resin is 5 to 30 wt %; And / or, the mass ratio of the polyurea and epoxy-modified silicone resin to the coating composition is 20 to 90:100, preferably 30 to 80:

100.

11. The method for preparing the modified organic silicon transition layer according to claim 9 or 10, characterized in that: include: The first component and the second component in the coating composition of the modified organic silicon transition layer according to any one of claims 1 to 7 are uniformly mixed to form a mixture, and then the mixture is applied to the surface of the substrate and reacted to obtain the modified organic silicon transition layer.

12. The preparation method according to claim 11, characterized in that: The NDJ-4 rotational viscosity of the mixture is 0.5-5.5 Pa.S, and the solid content of the mixture is above 55wt%; And / or, the ambient temperature when the mixture is applied to the substrate surface for reaction is -10-50°C; And / or, the reaction time when the mixture is applied to the surface of the substrate is 15 minutes to 24 hours.

13. A method for constructing an organosilicon-based antifouling coating on a substrate surface, characterized in that: include: Applying a primer composition at least once on the surface of a substrate to form a primer layer; The first component and the second component in the coating composition according to any one of claims 1 to 7 are mixed evenly, and applied to the surface of the primer layer for reaction to prepare a modified organic silicon transition layer; Furthermore, at least one layer of organosilicon-based antifouling coating or organosilicon hydrogel-based antifouling coating is coated on the modified organosilicon transition layer.

14. The method according to claim 13, characterized in that: The primer composition comprises any one or more combinations of an epoxy primer composition, a polyurethane / polyurea primer composition, and a silicone primer composition; And / or, the mixture formed by the first component and the second component is coated on the surface of the tie layer 1-4 times by coating; wherein the dry film thickness of a single coat is above 100 μm.

15. Use of the coating composition according to any one of claims 1 to 7 or the modified organic silicon transition layer according to any one of claims 9 to 10 in the field of antifouling engineering in a marine environment.

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