CN113004777A - Polyurea coating, coating and preparation method thereof - Google Patents

Polyurea coating, coating and preparation method thereof Download PDF

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Publication number
CN113004777A
CN113004777A CN202110150517.9A CN202110150517A CN113004777A CN 113004777 A CN113004777 A CN 113004777A CN 202110150517 A CN202110150517 A CN 202110150517A CN 113004777 A CN113004777 A CN 113004777A
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component
parts
polyurea coating
agent
coating
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CN113004777B (en
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李伟华
刘睿
曹文凯
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Sun Yat Sen University
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Sun Yat Sen University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02Polyureas
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide

Abstract

The invention discloses a polyurea coating, a coating and a preparation method thereof, and relates to the technical field of coatings. The polyurea coating comprises a component A, wherein the component A is a mixture of resin, pigment and filler and an auxiliary agent, and comprises the following components in parts by weight: 60-90 parts of organic fluorine-silicon modified polyaspartic ester resin, 20-40 parts of pigment and filler and 1-5 parts of auxiliary agent; the preparation method of the organic fluorine-silicon modified polyaspartic acid ester resin comprises the following steps: (1) mixing polyaspartic acid ester resin, gamma-aminopropyltrialkoxysilane and trifluoropropylmethyl cyclotrisiloxane, introducing inert gas, heating to 50-60 ℃ after 5-10min, and stirring and dropwise adding diethyl maleate to obtain a mixture; (2) and (3) keeping the temperature of the mixture to react for 8-16h, and cooling to obtain the organic fluorine-silicon modified polyaspartic acid resin.

Description

Polyurea coating, coating and preparation method thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a polyurea coating, a coating and a preparation method thereof.
Background
The waterproof coating material is a coating material which can prevent rainwater or groundwater from leaking out of a coating film formed by the coating material. There are two major classes of waterproof materials on the market today: firstly, polyurethane waterproof paint, but when the paint is used, organic solvent such as toluene, xylene and the like is generally adopted for dilution, so that toxicity is also contained; the other type is polymer cement-based waterproof paint which consists of emulsion synthesized by a plurality of water-based polymers and high-quality cement mixed with various additives, and the flexibility of the polymer (resin) and the rigidity of the cement are integrated, so that the waterproof paint has excellent impermeability and stability, but the current polymer cement-based paint has the problems of poor mechanical property and poor weather resistance.
The polyurea coating is a novel high-efficiency coating generated by the reaction of an isocyanate compound and an amine compound, has better tensile strength, wear resistance, impact resistance, chemical corrosion resistance and water resistance, and is widely applied to the fields of protection, concrete protection coating, waterproof coating, mechanical and automobile coating, wood paint, anticorrosive coating and the like. In particular to the waterproof field, the polyurea coating has great application value in the waterproof field due to the characteristic of compactness, theoretically, the C-N bond in the polyurea material is more stable than the C-O bond in the polyurethane, and the hydrolysis resistance and the hydrophobicity of the amine-terminated polyether are stronger than those of hydroxyl polyether, so that the performance of the polyurea coating is better in the aspect of waterproof coating.
The polyaspartic ester coating is an aliphatic coating with slow reaction, high weather resistance and high performance developed in the field of polyurea in recent years, and is called third-generation polyurea, but the polyaspartic ester coating on the market at present has the defects of poor color retention, high reaction speed, insufficient hydrophobicity and the like. Therefore, the polyaspartic acid ester resin is modified, the mechanical property and the hydrophobicity of the coating are improved, and the coating has great application potential.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide the polyurea coating with good hydrophobicity, prolonged curing time, high compactness and good aging resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the polyurea coating comprises a component A, wherein the component A is a mixture of resin, pigment and filler and an auxiliary agent, and comprises the following components in parts by weight: 60-90 parts of organic fluorine-silicon modified polyaspartic ester resin, 20-40 parts of pigment and filler and 1-5 parts of auxiliary agent; the preparation method of the organic fluorine-silicon modified polyaspartic acid ester resin comprises the following steps:
(1) mixing polyaspartic acid ester resin, gamma-aminopropyltrialkoxysilane and trifluoropropylmethyl cyclotrisiloxane, introducing inert gas, heating to 50-60 ℃ after 5-10min, and stirring and dropwise adding diethyl maleate to obtain a mixture;
(2) and (3) keeping the temperature of the mixture to react for 8-16h, and cooling to obtain the organic fluorine-silicon modified polyaspartic acid resin.
According to the invention, through a specific modification method, the polyaspartic acid ester resin is subjected to organic fluorine-silicon modification, and siloxane and C-F bonds are grafted on the polyaspartic acid ester resin, so that the bond energy of the resin is greatly improved, the stability, especially the light resistance, of the resin is improved, the light and color retention, the weather resistance and the hydrophobicity of the resin are increased, and the polyurea coating with good hydrophobicity, long curing time, high compactness and good aging resistance is prepared by applying the polyurea coating to the polyurea coating.
Further preferably, the component A comprises the following components in parts by weight: 60-80 parts of organic fluorine-silicon modified polyaspartic ester resin, 30-40 parts of pigment and filler and 2-3 parts of auxiliary agent.
The inventor shows through a great deal of creative research that the component A provided by the organic fluorine-silicon modified polyaspartic acid ester resin, the pigment and filler and the auxiliary agent through the combination of the weight parts has better hydrophobicity.
More preferably, the component A comprises the following components in parts by weight: 70 parts of organic fluorine-silicon modified polyaspartic acid ester resin, 35 parts of pigment and filler and 2 parts of auxiliary agent.
Preferably, the pigment filler is a mixture of titanium dioxide, bentonite and talcum powder, wherein the mass ratio of the titanium dioxide to the bentonite to the talcum powder is as follows: titanium dioxide: bentonite: talc powder 1: 1: 1-2. Titanium dioxide is a white pigment that is considered to be the best performing in the world today, with no toxicity, optimal opacity, optimal whiteness and brightness. The titanium dioxide has strong adhesive force, is not easy to chemically change and is always snow white. The function of covering power is achieved; the bentonite can form gel in various organic solvents, oils and liquid resins, has good thickening property, thixotropy, suspension stability, high-temperature stability, lubricity, film-forming property, water resistance and chemical stability, and has important application value in the paint industry; the talcum powder has excellent physical and chemical properties such as lubricity, fire resistance, acid resistance, insulativity, high melting point, chemical inactiveness, good covering power, softness, good luster, strong adsorption power and the like, and because the crystal structure of the talcum powder is layered, the talcum powder can sing a path of corrosion-retarding particles, play a role in shielding and increase the anticorrosion effect.
Preferably, the auxiliary agent is a mixture of a dispersing agent, a leveling agent, an antifoaming agent, a thixotropic agent and a silane coupling agent, wherein the mass ratio of the dispersing agent to the leveling agent to the antifoaming agent to the thixotropic agent to the silane coupling agent is as follows: dispersing agent: leveling agent: defoaming agent: thixotropic agent: the silane coupling agent is 1:0.5-1:0.5-1:1-2: 1-2. Wherein the dispersant is at least one of BYK9076, Surfynol CT-136 and ECO-2111, the leveling agent is at least one of BYK346, Sago 3277 and JH-9565, the defoaming agent is at least one of B-943, GP330 and SF808, the thixotropic agent is at least one of LV, KMT-40 and BYK-410, and the silane coupling agent is KH560, and the dispersant, the leveling agent and the defoaming agent are common commercial products.
Preferably, the polyurea coating further comprises a component B, wherein the component B is a curing agent and comprises the following components in parts by weight: 50-80 parts of isocyanate curing agent and 20-30 parts of HDI tripolymer; the isocyanate curing agent has high viscosity and short curing time, and is mixed with the HDI tripolymer curing agent. Combines the advantages of two curing agents, and has moderate viscosity and moderate curing time.
More preferably, the isocyanate curing agent is at least one of C-HXR, Hensman 2020 and HB-175; the HB-175 product model is Basonat HB175 MP/X, supplied by Pasteur, Germany; the Hensmei 2020 polyisocyanate curing agent is provided by Shanghai Kayin chemical industry; C-HXR is supplied by Tosoh, Japan. The HDI trimer curing agent is at least one of N-3390, CORONATE 2384 and N-75. Wherein, N-3390 and N-75 are provided for Germany Bayer; CORONATE 2384 is provided by eastern Japanese.
Preferably, the weight ratio of the A component to the B component is: the component A comprises: the component B is 1-2: 1-2.
Further preferably, the weight ratio of the A component to the B component is: the component A comprises: and the component B is 1: 1.
Meanwhile, the invention also provides a polyurea coating containing the polyurea coating.
The polyurea coating provided by the invention creatively mixes the component A and the component B of the specific component to prepare the polyurea coating which has the characteristics of compactness, continuity and no seam and has the characteristic of hydrophobicity of fluororesin.
Furthermore, the invention also provides application of the polyurea coating in the fields of waterproof engineering such as large-scale building structures, chemical infrastructure, water conservancy and the like.
In addition, the invention also provides a preparation method of the polyurea coating, which comprises the following steps:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the polyurea coating;
(2) and (2) uniformly mixing the polyurea coating obtained in the step (1), and spraying, manually brushing or rolling the polyurea coating on metal within 80-100min to obtain the polyurea coating.
Compared with the prior art, the invention has the beneficial effects that: (1) the invention carries out fluorine-silicon modification on the polyaspartic acid ester resin, and improves the light and color retention, weather resistance and hydrophobicity of the resin by grafting siloxane and C-F bonds on the polyaspartic acid ester resin; (2) the activity of the fluorine-silicon modified polyaspartic ester molecules is greatly reduced compared with that of primary amino groups due to the secondary amine groups, and the diester groups contained in the polyaspartic ester are compatibilized, so that the fluorine-silicon modified polyaspartic ester and the organic polymer containing isocyanate functional groups can react stably and are well compatible, and the compactness and the construction convenience of the coating are improved; (3) the polyurea coating disclosed by the invention has the characteristics of compactness, continuity and no seam of the polyurea coating, has the characteristic of fluororesin hydrophobicity, and has an excellent waterproof effect.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Examples 1-5 are set forth herein, and the selection of the components and parts by weight of specific examples 1-5 are shown in tables 1 and 2, and all products used herein are commercially available:
TABLE 1 selection of Components for specific examples 1-5
Figure BDA0002930541250000041
Figure BDA0002930541250000051
Figure BDA0002930541250000061
TABLE 2 selection of parts by weight of specific examples 1-5
Figure BDA0002930541250000062
The preparation of the polyurea coatings described in the examples, after weighing the components according to tables 1 and 2, comprises the following steps:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the polyurea coating;
(2) and (2) uniformly mixing the polyurea coating obtained in the step (1), and spraying, manually brushing or rolling the polyurea coating on metal within 90min to obtain the polyurea coating.
In the component A, the preparation method of the organic fluorine-silicon modified polyaspartic acid ester resin comprises the following steps:
(1) mixing polyaspartic acid ester resin, gamma-aminopropyltrialkoxysilane and trifluoropropylmethyl cyclotrisiloxane, introducing inert gas, heating to 55 ℃ after 5min, and stirring and dropwise adding diethyl maleate to obtain a mixture;
(2) and (3) carrying out heat preservation reaction on the mixture for 10 hours at the temperature of 55 ℃, and cooling to obtain the organic fluorine-silicon modified polyaspartic acid resin.
Meanwhile, the application sets comparative examples, and specific comparative examples 1 to 4 are as follows:
in the component A of the comparative example 1, the resin is polyaspartic ester resin which is not modified by organic fluorine silicon, and the rest components, the parts by weight and the preparation method are completely the same as those of the component A of the example 5;
in the component A of the comparative example 2, the resin is organic fluorine-silicon modified epoxy resin, and the rest components, the parts by weight and the preparation method are completely the same as those of the component A of the example 5;
in the component B of the comparative example 3, the curing agent is isocyanate F-70D, and the rest components, the parts by weight and the preparation method are completely the same as those of the component B of the example 5;
comparative example 4 is a commercially available polyurea coating (Jindingtai JDT-006) prepared as a coating and then subjected to comparative testing
Test examples Performance test
And (4) testing standard: as shown in table 3:
and (3) testing results: as shown in table 3:
TABLE 3 results of performance test of examples and comparative examples
Figure BDA0002930541250000071
Figure BDA0002930541250000081
As can be seen from table 3, the polyurea coating modified by fluorosilicone and prepared by matching the curing agent with isocyanate with different viscosities has excellent performance, and the indexes of aging resistance, flexibility, elongation at break, tensile strength, tear strength, water absorption, water impermeability and the like greatly exceed those of the polyurea coating which is not modified by fluorosilicone, fluorosilicone epoxy resin, and the curing agent which is single isocyanate and is sold in the market.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The polyurea coating is characterized by comprising a component A, wherein the component A is a mixture of resin, pigment and filler and auxiliaries and comprises the following components in parts by weight: 60-90 parts of organic fluorine-silicon modified polyaspartic ester resin, 20-40 parts of pigment and filler and 1-5 parts of auxiliary agent; the preparation method of the organic fluorine-silicon modified polyaspartic acid ester resin comprises the following steps:
(1) mixing polyaspartic acid ester resin, gamma-aminopropyltrialkoxysilane and trifluoropropylmethyl cyclotrisiloxane, introducing inert gas, heating to 50-60 ℃ after 5-10min, and stirring and dropwise adding diethyl maleate to obtain a mixture;
(2) and (3) keeping the temperature of the mixture to react for 8-16h, and cooling to obtain the organic fluorine-silicon modified polyaspartic acid resin.
2. The polyurea coating of claim 1, wherein the a component comprises the following parts by weight of components: 60-80 parts of organic fluorine-silicon modified polyaspartic ester resin, 30-40 parts of pigment and filler and 2-3 parts of auxiliary agent.
3. The polyurea coating of claim 2, wherein the a component comprises the following parts by weight of components: 70 parts of organic fluorine-silicon modified polyaspartic acid ester resin, 35 parts of pigment and filler and 2 parts of auxiliary agent.
4. The polyurea coating according to any one of claims 1 to 3, wherein the pigment and filler is a mixture of titanium dioxide, bentonite and talc, wherein the mass ratio of titanium dioxide, bentonite and talc is: titanium dioxide: bentonite: talc powder 1: 1: 1-2.
5. The polyurea coating according to any one of claims 1 to 3, wherein the additive is a mixture of a dispersant, a leveling agent, an antifoaming agent, a thixotropic agent and a silane coupling agent, wherein the mass ratio of the dispersant, the leveling agent, the antifoaming agent, the thixotropic agent and the silane coupling agent is: dispersing agent: leveling agent: defoaming agent: thixotropic agent: the silane coupling agent is 1:0.5-1:0.5-1:1-2: 1-2.
6. The polyurea coating of claim 1, further comprising a B component, wherein the B component is a curing agent comprising the following components in parts by weight: 50-80 parts of isocyanate curing agent and 20-30 parts of HDI tripolymer.
7. The polyurea coating of claim 6, wherein the weight ratio of the A component to the B component is: the component A comprises: the component B is 1-2: 1-2.
8. The polyurea coating of claim 7, wherein the weight ratio of the a component to the B component is: the component A comprises: and the component B is 1: 1.
9. A polyurea coating comprising the polyurea coating of claim 7 or 8.
10. The method of preparing a polyurea coating according to claim 9, comprising the steps of:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the polyurea coating;
(2) and (2) uniformly mixing the polyurea coating obtained in the step (1), and spraying, manually brushing or rolling the polyurea coating on metal within 80-100min to obtain the polyurea coating.
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Cited By (5)

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CN114196304A (en) * 2022-01-08 2022-03-18 深圳飞扬骏研新材料股份有限公司 Solvent-free fluorine-modified polyaspartic acid ester multifunctional heat-insulating coating
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CN115651528A (en) * 2022-10-10 2023-01-31 中车南京浦镇车辆有限公司 Environment-friendly self-cleaning modified polyaspartic acid ester coating and preparation method thereof
CN116042070A (en) * 2023-03-01 2023-05-02 山东卓高新材料有限公司 Self-repairing polyaspartic acid ester polyurea waterproof coating and preparation method thereof
WO2023240945A1 (en) * 2022-06-17 2023-12-21 中车株洲车辆有限公司 Polyurea coating and preparation method therefor

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114231142A (en) * 2021-12-31 2022-03-25 石家庄戴克科技有限公司 Novel fluorine-silicon modified polyurea material and preparation method thereof
CN114196304A (en) * 2022-01-08 2022-03-18 深圳飞扬骏研新材料股份有限公司 Solvent-free fluorine-modified polyaspartic acid ester multifunctional heat-insulating coating
WO2023240945A1 (en) * 2022-06-17 2023-12-21 中车株洲车辆有限公司 Polyurea coating and preparation method therefor
CN115651528A (en) * 2022-10-10 2023-01-31 中车南京浦镇车辆有限公司 Environment-friendly self-cleaning modified polyaspartic acid ester coating and preparation method thereof
CN116042070A (en) * 2023-03-01 2023-05-02 山东卓高新材料有限公司 Self-repairing polyaspartic acid ester polyurea waterproof coating and preparation method thereof

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