CN113045990A - Solvent-free super-wear-resistant elastic anticorrosive paint - Google Patents
Solvent-free super-wear-resistant elastic anticorrosive paint Download PDFInfo
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Abstract
The invention discloses a solvent-free super-wear-resistant elastic anticorrosive paint which is prepared from the following raw materials in parts by weight: 30-60 parts of elastic emulsion, 20-50 parts of lignin modified polyurea elastomer, 15-30 parts of thermoplastic resin, 10-20 parts of carboxyl modified functional filler, 8-15 parts of dispersing agent and 5-10 parts of carboxyl ultraviolet absorbent. The coating prepared by the invention has higher wear resistance, acid and alkali resistance and good ultraviolet resistance, and can adapt to a larger temperature range so that the coating does not deform and crack. The paint is not added with a solvent in the preparation process, does not release pollutants, and is safe, environment-friendly and pollution-free. Therefore, the coating prepared by the invention is suitable for general popularization and application in the coating industry.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a solvent-free super-wear-resistant elastic anticorrosive coating.
Background
The anticorrosive coating is generally divided into a conventional anticorrosive coating and a heavy anticorrosive coating, and is an essential coating in paint coatings. The conventional anticorrosive paint plays a role in corrosion resistance on metals and the like under general conditions, and protects the service life of nonferrous metals; the heavy-duty anticorrosive coating is an anticorrosive coating which can be applied in a relatively severe corrosive environment compared with a conventional anticorrosive coating and has a longer protection period than the conventional anticorrosive coating.
For the anticorrosive paint, the requirement on the performance of the product is continuously improved, and the requirement on the corrosion protection of a substrate is higher and higher, however, the traditional anticorrosive paint cannot meet the current use requirement. The cost of individual performance is high, the cost performance of the coating is reduced, a certain environmental pollution risk exists due to the fact that a part of the coating contains heavy metals or toxic substances such as lead, zinc or chromate, a large amount of non-renewable resources are consumed, and the sustainable development of society and economy is not facilitated. Therefore, the development of various novel long-acting environment-friendly anticorrosive coatings is always a hot problem of research.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a solvent-free super wear-resistant elastic anticorrosive paint.
In order to achieve the purpose, the invention provides the following technical scheme:
the solvent-free super-wear-resistant elastic anticorrosive paint is prepared from the following raw materials in parts by weight:
30-60 parts of elastic emulsion, 20-50 parts of lignin modified polyurea elastomer, 15-30 parts of thermoplastic resin, 10-20 parts of carboxyl modified functional filler, 8-15 parts of dispersant and 5-10 parts of carboxyl ultraviolet absorbent;
wherein the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the functional filler to the hydroxyapatite is (3-8): (2-5): (1-4): (1-3): (2-6): (2-4).
Further, the preparation method of the lignin-modified polyurea elastomer comprises the following steps:
(1) using 90wt% acetic acid and sulfuric acid as a catalyst, using a feed liquid ratio of 1 (3-8) to cook eucalyptus pieces for 2-5h, separating coarse pulp and cooking liquor by reduced pressure filtration, concentrating the cooking liquor by 10 times, adding the concentrated cooking liquor into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 5-10min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to enable the mass fraction of the lignin acetate to be 20-40%, then adding 1/4-1/2 of polyurea elastomer in the mass of the lignin solution, and stirring and reacting at the temperature of 80 ℃ for 1-3h to obtain the lignin modified polyurea elastomer.
Further, the thermoplastic resin comprises one or a combination of polytetrafluoroethylene, polystyrene or polyvinyl chloride.
Further, the carboxyl modified functional filler is a functional filler modified by using a carboxyl modified silane coupling agent.
Further, the preparation method of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 2-4h at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
Further, the dispersing agent comprises one or more of vinyl bis stearamide, glyceryl monostearate and glyceryl tristearate.
Further, the carboxyl ultraviolet absorbent is a carboxylated polyether organic silicon ultraviolet absorbent.
The preparation method of the anticorrosive paint comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting at the temperature of 40-60 ℃ for 30-50 min;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 20-40min, adding the dispersing agent, stirring and mixing for 2-4h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
Has the advantages that: the solvent-free super-wear-resistant elastic anticorrosive paint provided by the invention has high wear resistance, acid and alkali resistance and good ultraviolet resistance, and can adapt to a large temperature range, so that the paint is not deformed and cracked. The polyurea elastomer subjected to lignin modification treatment can further improve the wear resistance and mechanical strength of the polyurea elastomer, and the lignin surface contains a large number of hydroxyl groups, so that the lignin surface can be chemically crosslinked with the carboxyl-modified functional filler, the long-term crosslinking state of the functional filler and the matrix raw material is ensured, the functional filler is not precipitated, and the further improvement of the coating performance is ensured. The paint is not added with a solvent in the preparation process, does not release pollutants, and is safe, environment-friendly and pollution-free. Therefore, the coating prepared by the invention is suitable for general popularization and application in the coating industry.
Detailed Description
The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1
The solvent-free super-wear-resistant elastic anticorrosive paint is prepared from the following raw materials in parts by weight:
30 parts of elastic emulsion, 20 parts of lignin modified polyurea elastomer, 15 parts of thermoplastic resin, 10 parts of carboxyl modified functional filler, 8 parts of dispersant and 5 parts of carboxyl ultraviolet absorbent;
the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the barite powder to the kaolin to the nano titanium dioxide to the zinc oxide is 3:2:1:1: 2.
The preparation method of the lignin modified polyurea elastomer comprises the following steps:
(1) boiling eucalyptus pieces for 2 hours by using 90wt% of acetic acid and a sulfuric acid as a catalyst according to a feed-liquid ratio of 1:3, separating coarse pulp and a boiling liquid by reduced pressure filtration, concentrating the boiling liquid by 10 times, adding the boiling liquid into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 5min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to enable the mass fraction of the lignin acetate to be 20%, then adding 1/4 polyurea elastomer in the mass of the lignin solution, and stirring and reacting for 1h at the temperature of 80 ℃ to obtain the lignin modified polyurea elastomer.
The thermoplastic resin is polytetrafluoroethylene.
The carboxyl modified functional filler is modified by using a carboxyl modified silane coupling agent.
The preparation method of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 2h at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
The dispersing agent is vinyl bis stearamide.
The carboxyl ultraviolet absorbent is a carboxylated polyether organic silicon ultraviolet absorbent (the preparation method of the compound is described in detail in the synthesis, characterization and application of the carboxylated polyether organic silicon ultraviolet absorbent CPE-MUVS, the fine chemical industry, volume 28, stage 12).
The preparation method of the anticorrosive paint comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting at the temperature of 40 ℃ for 30 min;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 20min, adding the dispersing agent, stirring and mixing for 2h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
Example 2
The solvent-free super-wear-resistant elastic anticorrosive paint is prepared from the following raw materials in parts by weight:
45 parts of elastic emulsion, 35 parts of lignin modified polyurea elastomer, 22 parts of thermoplastic resin, 15 parts of carboxyl modified functional filler, 12 parts of dispersing agent and 7 parts of carboxyl ultraviolet absorbent;
the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the barite powder to the kaolin to the zinc oxide to the mica powder is 5:3: 2:4: 3.
The preparation method of the lignin modified polyurea elastomer comprises the following steps:
(1) boiling eucalyptus pieces for 4 hours by using 90wt% of acetic acid and a sulfuric acid as a catalyst according to a feed-liquid ratio of 1:5, separating coarse pulp and a boiling liquid by reduced pressure filtration, concentrating the boiling liquid by 10 times, adding the boiling liquid into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 6min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to ensure that the mass fraction of the lignin acetate is 30%, then adding 1/3 polyurea elastomer in the mass of the lignin solution, and stirring and reacting for 2 hours at the temperature of 80 ℃ to obtain the lignin modified polyurea elastomer.
The thermoplastic resin is polytetrafluoroethylene and polystyrene with the mass ratio of 1: 1.
The carboxyl modified functional filler is modified by using a carboxyl modified silane coupling agent.
The preparation method of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 3h at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
The dispersing agent is vinyl bis stearamide, glyceryl monostearate and glyceryl tristearate in a mass ratio of 1:1: 1.
Further, the carboxyl ultraviolet absorbent is a carboxylated polyether organic silicon ultraviolet absorbent.
The preparation method of the anticorrosive paint comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting at the temperature of 50 ℃ for 40 min;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 30min, adding the dispersing agent, stirring and mixing for 3h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
Example 3
The solvent-free super-wear-resistant elastic anticorrosive paint is prepared from the following raw materials in parts by weight:
50 parts of elastic emulsion, 40 parts of lignin modified polyurea elastomer, 250 parts of thermoplastic resin, 18 parts of carboxyl modified functional filler, 13 parts of dispersing agent and 8 parts of carboxyl ultraviolet absorbent;
the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the functional filler to the hydroxyapatite is 6: 4:3:2:5: 3.
The preparation method of the lignin modified polyurea elastomer comprises the following steps:
(1) boiling eucalyptus pieces for 4 hours by using 90wt% of acetic acid and a sulfuric acid as a catalyst according to a feed-liquid ratio of 1:6, separating coarse pulp and a boiling liquid by reduced pressure filtration, concentrating the boiling liquid by 10 times, adding the boiling liquid into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 8min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to enable the mass fraction of the lignin acetate to be 20-40%, then adding 1/3 polyurea elastomer mass in the lignin solution, and stirring and reacting for 2.5h at the temperature of 80 ℃ to obtain the lignin modified polyurea elastomer.
The thermoplastic resin is polystyrene.
The carboxyl modified functional filler is modified by using a carboxyl modified silane coupling agent.
The preparation method of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 3.5h at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
The dispersant is stearic acid monoglyceride.
The carboxyl ultraviolet absorbent is a carboxylated polyether organic silicon ultraviolet absorbent.
The preparation method of the anticorrosive paint comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting for 45min at the temperature of 55 ℃;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 35min, adding the dispersing agent, stirring and mixing for 3.5h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
Example 4
The solvent-free super-wear-resistant elastic anticorrosive paint is prepared from the following raw materials in parts by weight:
60 parts of elastic emulsion, 50 parts of lignin modified polyurea elastomer, 30 parts of thermoplastic resin, 20 parts of carboxyl modified functional filler, 15 parts of dispersing agent and 10 parts of carboxyl ultraviolet absorbent;
the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the functional filler to the hydroxyapatite is 8: 5:4: 3: 6: 4.
The preparation method of the lignin modified polyurea elastomer comprises the following steps:
(1) boiling eucalyptus pieces for 5 hours by using 90wt% of acetic acid and a sulfuric acid as a catalyst according to a feed-liquid ratio of 1:8, separating coarse pulp and a boiling liquid by reduced pressure filtration, concentrating the boiling liquid by 10 times, adding the boiling liquid into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 10min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to enable the mass fraction of the lignin acetate to be 40%, then adding 1/2 polyurea elastomer in the mass of the lignin solution, and stirring and reacting for 3 hours at the temperature of 80 ℃ to obtain the lignin modified polyurea elastomer.
The thermoplastic resin is polyvinyl chloride.
The carboxyl modified functional filler is modified by using a carboxyl modified silane coupling agent.
The preparation method of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 4 hours at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
The dispersant is glyceryl tristearate.
The carboxyl ultraviolet absorbent is a carboxylated polyether organic silicon ultraviolet absorbent.
The preparation method of the anticorrosive paint comprises the following steps:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting at the temperature of 60 ℃ for 50 min;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 40min, adding the dispersing agent, stirring and mixing for 4h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
Comparative example 1
Comparative example 1 differs from example 2 in that the polyurea elastomer has not been subjected to a lignin modification treatment.
Comparative example 2
Comparative example 2 differs from example 2 in that the functional filler is not carboxyl-modified.
The coatings obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to the following performance tests, and the results of the tests are shown in Table 1. As shown in Table 1, the coating prepared by the invention has high wear resistance, acid and alkali resistance and good ultraviolet resistance, and can adapt to a large temperature range without deformation or cracking. The coatings prepared in the comparative examples 1 and 2 have poor performance, and the wear resistance and the mechanical strength of the polyurea elastomer can be further improved mainly due to the polyurea elastomer subjected to lignin modification treatment, and the polyurea elastomer can be chemically crosslinked with the carboxyl modified functional filler due to the fact that the surface of lignin contains a large number of hydroxyl groups, so that the long-term crosslinking state of the functional filler and the matrix raw material is ensured without precipitation, and further improvement of the coating performance is ensured.
TABLE 1
Claims (8)
1. The solvent-free super-wear-resistant elastic anticorrosive paint is characterized by being prepared from the following raw materials in parts by weight:
30-60 parts of elastic emulsion, 20-50 parts of lignin modified polyurea elastomer, 15-30 parts of thermoplastic resin, 10-20 parts of carboxyl modified functional filler, 8-15 parts of dispersant and 5-10 parts of carboxyl ultraviolet absorbent;
wherein the functional filler comprises barite powder, kaolin, nano titanium dioxide, zinc oxide, mica powder and hydroxyapatite, and the mass ratio of the functional filler to the hydroxyapatite is (3-8): (2-5): (1-4): (1-3): (2-6): (2-4).
2. The solvent-free super wear-resistant elastic anticorrosive paint as claimed in claim 1, wherein the preparation method of the lignin-modified polyurea elastomer comprises the following steps:
(1) using 90wt% acetic acid and sulfuric acid as a catalyst, using a feed liquid ratio of 1 (3-8) to cook eucalyptus pieces for 2-5h, separating coarse pulp and cooking liquor by reduced pressure filtration, concentrating the cooking liquor by 10 times, adding the concentrated cooking liquor into deionized water for precipitation, standing overnight, performing vacuum filtration, washing a filter cake with hot water, and freeze-drying the filter cake to obtain acetic acid lignin;
(2) dissolving amine-terminated polyether D2000 in a solvent N, N-dimethylacetamide, slowly dripping into a three-neck flask containing diphenylmethane diisocyanate, stirring at room temperature for prepolymerization for 30min, adding the solvent in which a chain extender dimethylthio toluene diamine is dissolved into the flask, and continuously stirring the solution for 5-10min to obtain the synthesized polyurea elastomer;
(3) weighing lignin acetate, dissolving the lignin acetate in an N, N-dimethylacetamide solution to enable the mass fraction of the lignin acetate to be 20-40%, then adding 1/4-1/2 of polyurea elastomer in the mass of the lignin solution, and stirring and reacting at the temperature of 80 ℃ for 1-3h to obtain the lignin modified polyurea elastomer.
3. The solvent-free elastic anticorrosive paint with super wear resistance as claimed in claim 1, wherein the thermoplastic resin includes one or more of polytetrafluoroethylene, polystyrene and polyvinyl chloride.
4. The solvent-free elastic anticorrosive paint with super wear resistance of claim 1, wherein the carboxyl modified functional filler is a functional filler modified with a carboxyl modified silane coupling agent.
5. The solvent-free elastic anticorrosive paint with super wear resistance as claimed in claim 1, wherein the preparation process of the carboxyl modified silane coupling agent comprises the following steps: dissolving 15g of gamma-aminopropyltriethoxysilane, 10g of succinic anhydride and 5mL of triethylamine in 80mL of ethyl acetate, and heating and refluxing for 2-4h at 80 ℃; then, the organic solvent is removed by distillation under reduced pressure to obtain the carboxyl-modified silane coupling agent.
6. The solvent-free elastic wear-resistant anticorrosive coating according to claim 1, wherein the dispersant comprises one or more of vinyl bis-stearamide, glyceryl monostearate and glyceryl tristearate.
7. The solvent-free elastic anticorrosive paint with super wear resistance of claim 1, wherein the carboxyl ultraviolet absorbent is carboxylated polyether organic silicon ultraviolet absorbent.
8. The method for preparing the anticorrosive paint according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) weighing the raw materials in parts by weight;
(2) heating and softening the thermoplastic resin, adding the lignin modified polyurea elastomer, the carboxyl modified functional filler and the carboxyl ultraviolet absorbent, and reacting at the temperature of 40-60 ℃ for 30-50 min;
(3) and (3) adding the elastic emulsion into the solution obtained after the reaction in the step (2), stirring and reacting for 20-40min, adding the dispersing agent, stirring and mixing for 2-4h, and thus obtaining the solvent-free super wear-resistant elastic anticorrosive paint.
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