CN111484619A - Silane prepolymer, anticorrosive coating and application thereof - Google Patents
Silane prepolymer, anticorrosive coating and application thereof Download PDFInfo
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Abstract
The invention discloses a silane prepolymer, an anticorrosive coating and application thereof, wherein the silane prepolymer is composed of 10-55 wt% of alkyl trialkoxysilane containing an epoxy group and 15-75 wt% of alkyl alkoxy silane, the anticorrosive coating is composed of the silane prepolymer, epoxy resin, pigment and filler, an amine curing agent, an aminosilane coupling agent, a solvent and a coating additive, and the anticorrosive coating is applied to a humid and condensation environment. The anticorrosive coating is prepared from silane prepolymer, and an anticorrosive coating formed by the anticorrosive coating contains an organic-inorganic hybrid structure and forms a chemical bond in a coating/metal interface, so that high adhesive force can be kept for a long time in a water-immersion, humid and condensation environment, the conditions of rapid attenuation, foaming, peeling and the like of the adhesive force of a common anticorrosive coating in the environment are avoided, the water vapor permeability of the coating is low, and the anticorrosive performance is high.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a silane prepolymer, an anticorrosive coating and application thereof.
Background
In chemical and marine environments, some equipment is kept moist on the surface of the equipment for a long time due to the fact that the working temperature of the equipment is lower than the dew point, and condensation and dripping phenomena are accompanied. For example, the main natural gas transmission pipeline is mostly buried pipelines, the underground temperature is generally lower than the ground temperature in spring, summer and autumn, the natural gas transmission station, the branch transmission valve chamber and the block valve chamber are located above the ground, and when low-temperature natural gas flows through the above-ground parts, the surface temperature of the pipeline is lower than the dew point, so that a long-term condensation environment is formed. Meanwhile, when the pressure of natural gas is reduced, the temperature of the natural gas is reduced, and once the temperature of the surface of the pipeline is lower than the dew point, condensation can be formed on the surface of the pipeline. The coating coated on the surface of the pipeline is always in a water film soaking state, so that the adhesive force of the coating is reduced, corrosion is formed at the weak part of the paint film, and the protective effect on the natural gas pipeline is gradually lost. Thus, the condensation environment presents a major challenge to the long-term effective corrosion protection of natural gas pipelines. For example, some sections in a chemical plant need cooling, part of fluid has low temperature, such as liquid ammonia, the surface temperature of equipment is lower than the dew point, and a water film exists for a long time, so that the adhesion of a paint film of an anti-corrosion coating is difficult to maintain, and the safety of the equipment is difficult to ensure in a severe corrosion environment of the chemical plant.
In the prior art, trialkoxysilane coupling agents containing epoxy groups are used as adhesion promoters all the time, so that the wet adhesion of a paint film is improved. However, in the case of an anticorrosive coating composition using an epoxy group-containing trialkoxysilane coupling agent as an adhesion promoter, there are problems of low coupling efficiency, poor storage stability, and the like in practical use, and thus there is a strong demand for a silane polymer having high compatibility with a host resin and higher functionality of a coupling group to exhibit a more stable wet adhesion promoting effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a silane prepolymer, an anticorrosive coating and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a silane prepolymer comprising 10 to 55 wt% of an epoxy group-containing alkyltrialkoxysilane and 15 to 75 wt% of an alkylalkoxysilane, wherein the epoxy group-containing alkyltrialkoxysilane is represented by formula (1), and the alkylalkoxysilane is represented by formula (2):
R1Si(OR2)(OR3)(OR4)(1)；
in the formula (1), R1Is an epoxy-containing organic radical, R2～R4Respectively one of methyl, ethyl, propyl, isopropyl, butyl and isobutyl;
Si(R5)(R6)(R7)(R8)(2)；
in the formula (2), R5～R8Respectively one of alkyl, aryl alkyl alkoxy and aryloxy.
Preferably, the degree of hydrolysis of the silane prepolymer is 40 to 90 wt%. The degree of hydrolysis of the silane prepolymer in this range will balance reaction rate and storage stability.
The invention also discloses an anticorrosive coating which is composed of a silane prepolymer, epoxy resin, pigment and filler, an amine curing agent, an aminosilane coupling agent, a solvent and a coating additive.
Preferably, the content of the epoxy resin in the anticorrosive coating is 15-50 wt%, the epoxy resin is one or a combination of liquid bisphenol A epoxy resin and liquid bisphenol F epoxy resin, and the number average molecular weight of the epoxy resin is lower than 700.
Preferably, the content of the pigment and the filler in the anticorrosive coating is 20-50 wt%. In the above technical scheme, the pigment and filler are pigments and fillers known in the paint industry, and commonly used pigments and fillers include titanium dioxide, iron oxide yellow, iron oxide red, graphene, phthalocyanine green, phthalocyanine blue, permanent red, barium sulfate, mica powder, talc powder, quartz powder, feldspar powder, calcium carbonate, and the like.
Preferably, the content of the amine curing agent in the anticorrosive coating is 5-50 wt%, and the amine curing agent is one or more of alicyclic amine curing agent, fatty amine curing agent, phenolic amine epoxy curing agent, polyamide curing agent and amidoamine curing agent.
Preferably, the content of the aminosilane coupling agent in the anticorrosive paint is 0.1-10 wt%, in the technical scheme, the aminosilane coupling agent E is one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (β -aminoethyl) -3-aminopropylmethyldimethoxysilane, N-cyclohexyl-gamma-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, bis- [ gamma- (triethoxysilyl) -propyl ] -amine, N-N-butyl-gamma-aminopropyltriethoxysilane, N-N-butyl-gamma-aminopropyltrimethoxysilane and gamma-aminopropylmethyldiethoxysilane.
Preferably, the content of the solvent in the anticorrosive paint is 0.1-10 wt%. In the above technical scheme, the solvent is known and commonly used in the paint industry, and comprises xylene, n-butanol, S-100# solvent, propylene glycol methyl ether, propylene glycol ethyl ether and the like, and the above solvents can be used singly or in combination of a plurality of solvents.
Preferably, the content of the coating additive in the anticorrosive coating is 0.1-10 wt%, and the coating additive is a dispersing agent, a leveling agent, an antifoaming agent or a rheological additive. In the above technical scheme, the dispersant includes polyacrylate dispersant or polyurethane dispersant; the leveling agent comprises an organic silicon leveling agent or an acrylate leveling agent and the like; the defoaming agent comprises an organic silicon defoaming agent or an acrylate defoaming agent and the like; the rheological aid comprises bentonite, fumed silica, polyamide wax, modified hydrogenated castor oil, etc.
The invention also discloses application of the anticorrosive coating, and the anticorrosive coating is applied to a humid and condensation environment.
The invention has the beneficial effects that:
the anticorrosive coating is prepared from silane prepolymer, and an anticorrosive coating formed by the anticorrosive coating contains an organic-inorganic hybrid structure and forms a chemical bond in a coating/metal interface, so that high adhesive force can be kept for a long time in a water-immersion, humid and condensation environment, the conditions of rapid attenuation, foaming, peeling and the like of the adhesive force of a common anticorrosive coating in the environment are avoided, the water vapor permeability of the coating is low, and the anticorrosive performance is high.
Drawings
FIG. 1 is a photograph of the test pull adhesion of the anticorrosion coating composition A in experiment 1 in the present invention;
FIG. 2 is a photograph of the anticorrosive coating composition A of the present invention after a salt spray test for 1000 hours.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The first embodiment is as follows:
a silane prepolymer of this example is characterized by: the epoxy-containing alkyl trialkoxysilane is composed of 10-55 wt% of epoxy-containing alkyl trialkoxysilane and 15-75 wt% of alkyl alkoxy silane, wherein the epoxy-containing alkyl trialkoxysilane is represented by a formula (1), and the alkyl alkoxy silane is represented by a formula (2):
R1Si(OR2)(OR3)(OR4) (1)；
in the formula (1), R1Is an epoxy-containing organic radical, R2～R4Respectively one of methyl, ethyl, propyl, isopropyl, butyl and isobutyl;
Si(R5)(R6)(R7)(R8) (2)；
in the formula (2), R5～R8Respectively one of alkyl, aryl alkyl alkoxy and aryloxy.
The alkyl trialkoxysilane containing epoxy groups is one or a combination of 3- (2, 3-epoxypropoxy) propyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl triethoxysilane and 3- (2, 3-epoxypropoxy) propyl methyl dimethoxysilane.
The alkyl alkoxy silane is one or more of methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, diphenyl diethoxy silane, diphenyl dimethoxy silane, methyl phenyl diethoxy silane and tetraethoxy silane.
Adding alkyl trialkoxysilane and alkyl alkoxy silane containing epoxy groups into a solvent for dilution, and adding 0.01-0.5 mol/L acidic aqueous solution for hydrolysis to obtain the silane prepolymer of the embodiment.
In this embodiment, the degree of hydrolysis of the silane prepolymer is 40 to 90 wt%.
Example two:
the anticorrosive coating of the embodiment is composed of a silane prepolymer, epoxy resin, pigment and filler, an amine curing agent, an aminosilane coupling agent, a solvent and a coating additive. The silane prepolymer of the embodiment is combined with epoxy resin, pigment and filler, amine curing agent, amino silane coupling agent, solvent and coating additive to exert excellent anti-corrosion effect.
In the embodiment, the content of the epoxy resin in the anticorrosive coating is 15-50 wt%, the epoxy resin is one or more of liquid bisphenol a epoxy resin and liquid bisphenol F epoxy resin, and the number average molecular weight of the epoxy resin is lower than 700.
In the embodiment, the content of the pigment and the filler in the anticorrosive coating is 20-50 wt%. The pigment and filler are pigments and fillers known in the paint industry, and commonly used pigments and fillers comprise titanium dioxide, iron oxide yellow, iron oxide red, graphene, phthalocyanine green, phthalocyanine blue, permanent red, barium sulfate, mica powder, talcum powder, quartz powder, feldspar powder, calcium carbonate and the like.
In the embodiment, the content of the amine curing agent in the anticorrosive coating is 5-50 wt%, and the amine curing agent is one or more of alicyclic amine curing agent, fatty amine curing agent, phenolic amine epoxy curing agent, polyamide curing agent and amidoamine curing agent.
In the embodiment, the content of the aminosilane coupling agent in the anticorrosive paint is 0.1-10 wt%, and the aminosilane coupling agent E is one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (β -aminoethyl) -3-aminopropylmethyldimethoxysilane, N-cyclohexyl-gamma-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, bis- [ gamma- (triethoxysilyl) -propyl ] -amine, N-N-butyl-gamma-aminopropyltriethoxysilane, N-N-butyl-gamma-aminopropyltrimethoxysilane and gamma-aminopropylmethyldiethoxysilane.
In the embodiment, the content of the solvent in the anticorrosive coating is 0.1-10 wt%. The solvent is known and commonly used in the paint industry and comprises xylene, n-butanol, S-100# solvent, propylene glycol methyl ether, propylene glycol ethyl ether and the like, and the above solvents can be used singly or in combination.
In the embodiment, the content of the coating additive in the anticorrosive coating is 0.1-10 wt%, and the coating additive is a dispersing agent, a leveling agent, an antifoaming agent or a rheological additive. The dispersant includes polyacrylate dispersant or polyurethane dispersant; the leveling agent comprises an organic silicon leveling agent or an acrylate leveling agent and the like; the defoaming agent comprises an organic silicon defoaming agent or an acrylate defoaming agent and the like; the rheological aid comprises bentonite, fumed silica, polyamide wax, modified hydrogenated castor oil, etc.
The anticorrosive coating of the present example includes two components of a main agent and a curing agent. The preparation method of the main agent comprises the following steps: uniformly mixing the silane prepolymer, the epoxy resin, the solvent and the dispersing agent, adding the pigment and filler, sanding to the required fineness, adding the defoaming agent, the flatting agent, the rheological aid and the like, uniformly dispersing, filtering and packaging. The manufacturing method of the curing agent comprises the following steps: and (3) uniformly mixing the amine curing agent, the aminosilane coupling agent and the solvent, filtering and packaging.
The anticorrosive coating of the embodiment is applied to a humid and condensation environment, and can achieve a good protection effect on a coated object.
The anticorrosive coating film can be formed by applying the anticorrosive coating material of the present embodiment to the surface of the object to be coated, and examples of the application method include brushing, spraying, dipping, flow coating, spin coating, and the like, and these application methods can be carried out by using one or two or more of them in combination. After coating, the coating is dried at room temperature, and the drying time may be determined depending on the conditions such as the thickness of the coating film and the atmospheric temperature.
The following experimental comparison verifies the service performance of the anticorrosive coating of the invention:
preparation example 1 (preparation of silane prepolymer, S-1):
a flask with a thermometer, a reflux condenser, a stirrer and a dropping funnel is added with a 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane 40 component, a phenyltrimethoxysilane 60 component and a propylene glycol methyl ether 20 component, the mixture is heated to 75 ℃ under nitrogen atmosphere, then a sulfuric acid solution (0.2 mol/L) 8.8 components are added dropwise for 2 hours, and after the dropwise addition is finished, the temperature is kept for 2 hours to obtain a transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 70%.
Preparation example 2 (preparation of silane prepolymer, S-2):
a flask provided with a thermometer, a reflux condenser, a stirrer and a dropping funnel is added with a 3- (2, 3-glycidoxy) propyltrimethoxysilane 30 component, a diphenyldiethoxysilane 70 component and a propylene glycol methyl ether 20 component, heated to 75 ℃ under nitrogen atmosphere, and then added with a sulfuric acid solution (0.5 mol/L) 4.8 component dropwise for 2 hours, after the dropwise addition is finished, the temperature is kept for 2 hours to obtain a transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 60%.
Preparation example 3 (preparation of silane prepolymer, S-3):
a flask with a thermometer, a reflux condenser, a stirrer and a dropping funnel is added with a 3- (2, 3-glycidoxy) propyltrimethoxysilane 30 component, a diphenyldiethoxysilane 70 component and a propylene glycol methyl ether 20 component, the mixture is heated to 75 ℃ under nitrogen atmosphere, then 6.8 components of sulfuric acid solution (0.5 mol/L) are added dropwise for 2 hours, and after the dropwise addition is finished, heat is preserved for 2 hours to obtain a transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 85%.
Comparative Experimental example 1 (preparation of silane prepolymer, H-1):
a flask with a thermometer, a reflux condenser, a stirrer and a dropping funnel is added with 3- (2, 3-glycidoxy) propyl trimethoxy silane 90 component, diphenyl diethoxy silane 10 component and propylene glycol methyl ether 20 component, heated to 75 ℃ under nitrogen atmosphere, and then added with sulfuric acid solution (0.3 mol/L) 3.3 component dropwise for 2 hours, after the dropwise addition is finished, the temperature is kept for 2 hours to obtain transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 30 percent.
Comparative Experimental example 2 (preparation of silane prepolymer, H-2):
a flask with a thermometer, a reflux condenser, a stirrer and a dropping funnel is added with 100 parts of 3- (2, 3-glycidoxy) propyltrimethoxysilane and 20 parts of propylene glycol monomethyl ether, the mixture is heated to 75 ℃ under nitrogen atmosphere, 8 parts of sulfuric acid solution (0.1 mol/L) is added dropwise for 2 hours, and after the dropwise addition is finished, heat is preserved for 2 hours to obtain a transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 70%.
Comparative Experimental example 3 (preparation of silane prepolymer, H-2):
100 parts of phenyltrimethoxysilane and 20 parts of propylene glycol methyl ether are added into a flask provided with a thermometer, a reflux condenser, a stirrer and a dropping funnel, the flask is heated to 75 ℃ under nitrogen atmosphere, 11 parts of sulfuric acid solution (0.1 mol/L) is added dropwise for 2 hours, and after the dropwise addition is finished, heat is preserved for 2 hours to obtain a transparent silane prepolymer solution, wherein the hydrolysis degree of the silane prepolymer is 80%.
The silane prepolymers prepared in the preparation examples 1 to 3 and the comparative experiment examples 1 to 3 are added with epoxy resin, pigment and filler, amine curing agent, aminosilane coupling agent, solvent and coating additive with equal components to prepare 6 groups of anticorrosive coating compositions, and the formula of the 6 groups of anticorrosive coating compositions is shown in the following table 1:
TABLE 1
6 sets of anticorrosive coating compositions were produced according to the raw material ratios in table 1, and the compositions were sequentially recorded as anticorrosive coating composition a, anticorrosive coating composition B, anticorrosive coating composition C, anticorrosive coating composition D, anticorrosive coating composition E, and anticorrosive coating composition F, and the 6 sets of anticorrosive coating compositions were subjected to performance test comparisons, respectively, as follows:
experiment 1 (dry adhesion):
6 groups of anticorrosive coating compositions are respectively coated on a 70X 150X 2mm sandblasted carbon steel plate, the dry film thickness is 100 mu m, and after drying for 7 days at the temperature of 25 ℃, the adhesion is tested according to the GB/T5210-2006 pull-open method.
Experiment 2 (wet adhesion, 40 ℃ 720 h):
6 groups of anticorrosive coating compositions are respectively coated on a 70 x 150 x 2mm sandblasted carbon steel plate, the dry film thickness is 100 mu m, after being dried for 7 days at the temperature of 25 ℃, the steel plate is put into three-stage water at the temperature of 40 ℃ for soaking for 720 hours, and after being adjusted for 2 hours at room temperature, the adhesion is tested according to a GB/T5210-2006 pull-open method.
Experiment 3 (wet adhesion, 40 ℃ 720 h):
6 groups of anticorrosive coating compositions are respectively coated on a 70 x 150 x 2mm sandblasted carbon steel plate, the dry film thickness is 100 mu m, after being dried for 7 days at the temperature of 25 ℃, the steel plate is put into three-stage water at the temperature of 80 ℃ for soaking for 240 hours, and after being adjusted for 2 hours at room temperature, the adhesion is tested according to a GB/T5210-2006 pull-open method.
Experiment 4(1000h salt spray test rear expansion erosion width)
6 groups of anticorrosive coating compositions were coated on a 70X 150X 2mm sandblasted carbon steel plate, the dry film thickness was 100 μm, after drying at 25 ℃ for 7 days, the salt spray test was carried out for 1000 hours in accordance with GB/T1771-2007, and the substrate corrosion width was measured after the paint film at the scribe line was removed.
Experiment 5 (adhesion after 1000h salt spray test):
6 groups of anticorrosive coating compositions are respectively coated on a 70 x 150 x 2mm sandblasted carbon steel plate, the dry film thickness is 100 mu m, after drying for 7 days at the temperature of 25 ℃, a 1000-hour salt spray test is carried out according to GB/T1771-2007, and after 2 hours of room temperature adjustment, the adhesion is tested according to GB/T5210-2006 pull method.
The data for each experiment are shown in table 2 below:
TABLE 2
As shown in the table 2, the anticorrosive coating compositions A to C still have excellent wet adhesion after being corroded by warm water, hot water and salt mist, and the anticorrosive coating compositions D to F have the adhesion of less than 5Mpa after being soaked by hot water and corroded by salt mist, so that when the silane prepolymer prepared in the preparation examples 1 to 3 is used as an anticorrosive coating ingredient, the anticorrosive coating has better corrosion resistance and adhesion.
FIG. 1 is a photograph of the anti-corrosive coating composition A in experiment 1 showing a test pull-out adhesion of 14.83 MPa; FIG. 2 is a photograph of the anticorrosive coating composition A of experiment 4 after a salt spray experiment for 1000 hours, wherein no blistering or peeling of the paint film occurs.
Simple substitutions without changing the inventive content of the present invention are considered to be the same. The embodiments are described in a progressive manner in the specification, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A silane prepolymer characterized by: the epoxy-containing alkyl trialkoxysilane is composed of 10-55 wt% of epoxy-containing alkyl trialkoxysilane and 15-75 wt% of alkyl alkoxy silane, wherein the epoxy-containing alkyl trialkoxysilane is represented by a formula (1), and the alkyl alkoxy silane is represented by a formula (2):
R1Si(OR2)(OR3)(OR4) (1)；
in the formula (1), R1Is an epoxy-containing organic radical, R2～R4Respectively one of methyl, ethyl, propyl, isopropyl, butyl and isobutyl;
Si(R5)(R6)(R7)(R8) (2)；
in the formula (2), R5～R8Respectively one of alkyl, aryl alkyl alkoxy and aryloxy.
2. A silane prepolymer according to claim 1, wherein: the hydrolysis degree of the silane prepolymer is 40-90 wt%.
3. An anticorrosive paint, which is characterized in that: the anticorrosion paint consists of the silane prepolymer in claim 2, epoxy resin, pigment and filler, amine curing agent, amino silane coupling agent, solvent and paint additive.
4. An anti-corrosion coating according to claim 3, characterized in that: the content of the epoxy resin in the anticorrosive paint is 15-50 wt%, and the epoxy resin is one or a combination of liquid bisphenol A epoxy resin and liquid bisphenol F epoxy resin.
5. An anti-corrosion coating according to claim 3 or 4, characterized in that: the content of the pigment and the filler in the anticorrosive coating is 20-50 wt%.
6. The anticorrosive coating according to claim 5, characterized in that: the content of the amine curing agent in the anticorrosive paint is 5-50 wt%, and the amine curing agent is one or a combination of alicyclic amine curing agent, aliphatic amine curing agent, phenolic amine epoxy curing agent, polyamide curing agent and amidoamine curing agent.
7. An anti-corrosion coating according to claim 3,4 or 6, characterized in that: the content of the amino silane coupling agent in the anticorrosive coating is 0.1-10 wt%.
8. The anticorrosive coating according to claim 7, characterized in that: the content of the solvent in the anticorrosive paint is 0.1-10 wt%.
9. An anticorrosion coating according to claim 3 or 4 or 6 or 8, characterized in that: the content of the coating additive in the anticorrosive coating is 0.1-10 wt%, and the coating additive is a dispersing agent or a leveling agent or a defoaming agent or a rheological additive.
10. Use of an anti-corrosion coating according to claim 9, characterized in that: applying an anticorrosion coating according to claim 9 to a wet, condensation environment.
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| CN202010294014.4A CN111484619A (en) | 2020-04-15 | 2020-04-15 | Silane prepolymer, anticorrosive coating and application thereof |
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| CN202010294014.4A CN111484619A (en) | 2020-04-15 | 2020-04-15 | Silane prepolymer, anticorrosive coating and application thereof |
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