CN110845944A - Organic-inorganic hybrid wear-resistant coating and preparation method thereof - Google Patents
Organic-inorganic hybrid wear-resistant coating and preparation method thereof Download PDFInfo
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- CN110845944A CN110845944A CN201911080335.8A CN201911080335A CN110845944A CN 110845944 A CN110845944 A CN 110845944A CN 201911080335 A CN201911080335 A CN 201911080335A CN 110845944 A CN110845944 A CN 110845944A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to an organic-inorganic hybrid wear-resistant coating and a preparation method thereof. The polycarbonate modified wear-resistant paint organic-inorganic hybrid wear-resistant paint comprises the following raw materials in parts by weight: 30-40 parts of nano silica sol, 20-30 parts of silane coupling agent, 1-2 parts of organic acid, 1-2 parts of hydroxyl-containing silicone oil, 5-10 parts of polycarbonate modified polyester and 5-10 parts of nano filler. The silane coupling agent is hydrolyzed under the action of organic acid, the surface of the alkaline nano silica sol is grafted and modified, and the alkaline nano silica sol is further subjected to organic-inorganic hybridization with polycarbonate modified polyester, so that the excellent characteristics of organic polymers and inorganic materials are integrated, the wear resistance and impact resistance are good while the mechanical properties and hardness are good, and a coating layer is thick and does not crack; in addition, the chemical bond with toughness and elasticity formed by the polycarbonate thermal grafting modified polyester is combined, so that the wear resistance and the impact resistance of the prepared coating are further improved, and the application range of the wear-resistant coating is effectively expanded.
Description
Technical Field
The invention relates to the technical field of polyurethane coatings, in particular to an organic-inorganic hybrid wear-resistant coating and a preparation method thereof.
Background
The improvement of the wear resistance of the coating can be realized through various channels, the first is to use a pure inorganic coating as the coating, namely the inorganic ceramic film coating, the atomic structure of the coating is similar to that of glass, the main component of the coating is silicon dioxide, and the wear resistance of the coating is realized through high material hardness and stronger atomic bond energy and covalent bond energy; another method is to use polycarbonate modified wear-resistant paint, which reduces or eliminates the friction force applied from the outside by using the stretching and shrinking of the linear polycarbonate modified resin system, so as to improve the wear resistance of the coating.
However, both the two coatings have obvious coating defects, the hardness of the inorganic ceramic film coating is usually more than 7H and can reach 9H at most, but the coatings have the defects of poor impact resistance and easy cracking when the thickness of the coatings exceeds 30 micrometers; the polycarbonate modified wear-resistant coating has the defects that the impact resistance is better due to the offline structure of the coating, the coating is thick and does not crack, but the hardness is poor, and the hardness is generally less than HB; the disadvantages of both coatings greatly limit the scope of their use.
Disclosure of Invention
Based on the above, the invention aims to provide an organic-inorganic hybrid wear-resistant coating which has the advantages of high hardness, good wear resistance, good impact resistance and difficult cracking of thick coating.
An organic-inorganic hybrid wear-resistant coating comprises the following raw materials in parts by weight: 30-40 parts of nano silica sol, 20-30 parts of silane coupling agent, 1-2 parts of organic acid, 1-2 parts of hydroxyl-containing silicone oil, 5-10 parts of polycarbonate modified polyester and 5-10 parts of nano filler; the polycarbonate modified polyester is obtained by thermal reaction of polycarbonate and a polyester resin monomer composition, wherein the polyester resin monomer composition comprises a carboxyl monomer and a hydroxyl monomer.
The organic-inorganic hybrid wear-resistant coating provided by the invention is prepared by hydrolyzing a silane coupling agent under the action of organic acid, carrying out surface grafting modification on alkaline nano silica sol, and further carrying out organic-inorganic hybrid with polycarbonate modified polyester, so that the wear-resistant coating is integrated with the excellent characteristics of organic polymers and inorganic materials, has good mechanical properties and hardness, is good in wear resistance and impact resistance, and does not crack when being thick; in addition, the chemical bond with toughness and elasticity formed by combining the polycarbonate thermal grafting modified polyester can weaken or eliminate the friction force applied from the outside through the stretching and the contraction of a system, further improves the wear resistance and the impact resistance of the prepared coating, and effectively expands the application range of the wear-resistant coating.
Further, the carboxyl monomer is selected from one or more of isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and adipic acid; the hydroxyl monomer is selected from one or more of trimethylolpropane, trimethylolethane, neopentyl glycol, methyl propylene glycol and 1, 6-hexanediol.
Further, the nano silica sol is a nano silica hydrosol with the solid content of 25-40%, and the particle size range of the nano silica is 5-30 nm.
Further, the pH range of the nano silica sol is 8-11. The solid content, the pH range and the particle size range of the nano silicon dioxide of the nano silica sol are adjusted, so that the hybridized coating has better wear resistance and hardness.
Further, the silane coupling agent is methyl trimethoxy silane or methyl triethoxy silane which can be hydrolyzed and has better reactivity with the surface of an inorganic substance.
Further, the organic acid is formic acid or acetic acid to promote hydrolysis.
Further, the nano filler is one or more of nano alumina, nano zirconia and silicon carbide.
Furthermore, the particle size of the nano filler is less than 5 mu m, and the wear resistance is good.
In addition, the invention also provides a preparation method of the organic-inorganic hybrid wear-resistant coating, which comprises the following specific operation steps:
s1, weighing the raw materials according to the formula in claim 1, sequentially adding the nano silica sol, the silane coupling agent, the organic acid and the hydroxyl-containing silicone oil into a reaction kettle, heating to 40-50 ℃ under the condition of the rotation speed of 300-500rpm, and carrying out heat preservation and dispersion;
s2, adding the polycarbonate modified polyester into the mixture obtained in the step S1 while dispersing under the rotation speed condition of 400-600rpm, heating to 70-80 ℃, and then carrying out heat preservation and dispersion under the rotation speed condition of 800-1200 rpm;
s3, cooling to 25-35 ℃, adding the nano filler while dispersing, and dispersing at the rotation speed of 1000-1500 rpm;
s4, filtering the mixture obtained in the step S3 to obtain the organic-inorganic hybrid wear-resistant coating.
Further, in the step S1, the heat preservation dispersion time is 3-4 h; in the step S2, the heat preservation dispersion time is 1.5-2 h; in step S3, the dispersion time is 20-30 min; in step S4, a filter bag with the diameter of 15-25 μm is used for filtering large particles to ensure that all components of the coating are uniformly dispersed.
The organic-inorganic hybrid wear-resistant coating provided by the invention is hydrolyzed under the action of organic acid by utilizing a silane coupling agent, surface grafting modification is carried out on alkaline nano silica sol, organic-inorganic hybridization is further carried out on the alkaline nano silica sol and polycarbonate modified polyester, nano fillers of nano alumina, nano zirconia and silicon carbide are added, the excellent characteristics of organic polymers and inorganic materials are integrated, the wear-resistant performance and the impact resistance are good while the mechanical performance and the hardness are good, and a coating layer is thick and does not crack; in addition, the chemical bond with toughness and elasticity formed by combining the polycarbonate thermal grafting modified polyester can weaken or eliminate the friction force applied from the outside through the stretching and the contraction of a system, further improves the wear resistance and the impact resistance of the prepared coating, and effectively expands the application range of the wear-resistant coating. The preparation method of the organic-inorganic hybrid wear-resistant coating is simple to operate, reasonable in process, low in temperature required by preparation, low in equipment requirement and low in production cost.
Detailed Description
Example 1
The embodiment of the invention relates to an organic-inorganic hybrid wear-resistant coating, which comprises the following raw materials in parts by weight: 30 parts of nano silica sol, 20 parts of silane coupling agent, 1 part of organic acid, 1 part of hydroxyl-containing silicone oil, 5 parts of polycarbonate modified polyester and 5 parts of nano filler.
Wherein the nano silica sol is a nano silica sol with the solid content of 25 percent, and the pH value of the nano silica sol is 8; the particle size of the nano silicon dioxide is 5 nm.
The silane coupling agent is methyl trimethoxy silane; the organic acid is formic acid; the nano filler is nano alumina particles with the particle size of less than 5 mu m.
The polycarbonate modified polyester is obtained by the thermal reaction of polycarbonate, isophthalic acid and trimethylolpropane.
Example 2
The embodiment provides an organic-inorganic hybrid wear-resistant coating, which comprises the following raw materials in parts by weight: 40 parts of nano silica sol, 30 parts of silane coupling agent, 2 parts of organic acid, 2 parts of hydroxyl-containing silicone oil, 10 parts of polycarbonate modified polyester and 10 parts of nano filler.
Wherein the nano silica sol is a nano silica sol with the solid content of 30 percent, and the pH value of the nano silica sol is 10; the particle size of the nano silicon dioxide is 15 nm.
The silane coupling agent is methyl triethoxysilane; the organic acid is acetic acid; the nano filler is nano zirconia particles with the particle size of less than 5 mu m.
The polycarbonate modified polyester is obtained by thermal reaction of polycarbonate, tetrahydrophthalic anhydride, trimethylolethane and 1, 6-hexanediol.
Example 3
The embodiment provides an organic-inorganic hybrid wear-resistant coating, which comprises the following raw materials in parts by weight: 35 parts of nano silica sol, 25 parts of silane coupling agent, 1.5 parts of organic acid, 1.5 parts of hydroxyl-containing silicone oil, 8 parts of polycarbonate modified polyester and 8 parts of nano filler.
Wherein the nano silica sol is a nano silica sol with solid content of 45%, and the pH value is 11; the particle size of the nano silicon dioxide is 30 nm.
The silane coupling agent is methyl triethoxysilane; the organic acid is formic acid; the nano filler is nano silicon carbide particles with the particle size of less than 5 mu m.
The polycarbonate modified polyester is obtained by the thermal reaction of polycarbonate, hexahydrophthalic anhydride, adipic acid and methyl propylene glycol.
Example 4
The embodiment provides a preparation method of an organic-inorganic hybrid wear-resistant coating, which is characterized by comprising the following specific operation steps:
s1, weighing the raw materials according to the formula in claim 1, sequentially adding the nano silica sol, the silane coupling agent, the organic acid and the hydroxyl-containing silicone oil into a reaction kettle, heating to 40-50 ℃ under the condition of the rotation speed of 300-500rpm, and carrying out heat preservation and dispersion for 3-4 h;
s2, adding the polycarbonate modified polyester into the mixture obtained in the step S1 while dispersing under the rotation speed condition of 400-600rpm, heating to 70-80 ℃, and then carrying out heat preservation and dispersion for 1.5-2h under the rotation speed condition of 800-1200 rpm;
s3, cooling to 25-35 ℃, adding the nano filler while dispersing, and dispersing for 20-30min at the rotation speed of 1500rpm which is 1000-;
s4, filtering the mixture obtained in the step S3 by using a filter bag with the diameter of 15-25 mu m to obtain the organic-inorganic hybrid wear-resistant paint.
Example 5
The performance of the organic-inorganic hybrid wear-resistant paint is tested, and the test result is shown in the table I:
| comparison of Performance | Inorganic ceramic film paint | Polycarbonate modified wear-resistant coating | Organic-inorganic hybrid wear-resistant coating |
| Wear resistance | More than 15000 times | > 10000 times | ＞15000 |
| Wear resistance | The weight loss rate of the coating film is more than 2 percent | The weight loss rate of the coating is less than 1 percent | The weight loss rate of the coating is less than 1.2 percent |
| Hardness of | ＞8H | B | 3H |
| Impact resistance | 0 | ＞50 | ＞20 |
The organic-inorganic hybrid wear-resistant coating provided by the invention has the advantages of good wear resistance and wear resistance, high hardness and good impact resistance, and can balance the hardness and the impact property of the coating when the wear resistance reaches the performance standard of the inorganic ceramic film coating.
The organic-inorganic hybrid wear-resistant coating provided by the invention is hydrolyzed under the action of organic acid by utilizing a silane coupling agent, surface grafting modification is carried out on alkaline nano silica sol, organic-inorganic hybridization is further carried out on the alkaline nano silica sol and polycarbonate modified polyester, nano fillers of nano alumina, nano zirconia and silicon carbide are added, the excellent characteristics of organic polymers and inorganic materials are integrated, the wear-resistant performance and the impact resistance are good while the mechanical performance and the hardness are good, and a coating layer is thick and does not crack; in addition, the chemical bond with toughness and elasticity formed by combining the polycarbonate thermal grafting modified polyester can weaken or eliminate the friction force applied from the outside through the stretching and the contraction of a system, further improves the wear resistance and the impact resistance of the prepared coating, and effectively expands the application range of the wear-resistant coating. The preparation method of the organic-inorganic hybrid wear-resistant coating is simple to operate, reasonable in process, low in temperature required by preparation, low in equipment requirement and low in production cost.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The organic-inorganic hybrid wear-resistant coating is characterized by comprising the following raw materials in parts by weight: 30-40 parts of nano silica sol, 20-30 parts of silane coupling agent, 1-2 parts of organic acid, 1-2 parts of hydroxyl-containing silicone oil, 5-10 parts of polycarbonate modified polyester and 5-10 parts of nano filler; the polycarbonate modified polyester is obtained by thermal reaction of polycarbonate and a polyester resin monomer composition, wherein the polyester resin monomer composition comprises a carboxyl monomer and a hydroxyl monomer.
2. The organic-inorganic hybrid wear-resistant coating according to claim 1, characterized in that: the carboxyl monomer is selected from one or more of isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and adipic acid; the hydroxyl monomer is selected from one or more of trimethylolpropane, trimethylolethane, neopentyl glycol, methyl propylene glycol and 1, 6-hexanediol.
3. The organic-inorganic hybrid wear-resistant coating according to claim 1, characterized in that: the nano silica sol is nano silica hydrosol with solid content of 25-40%, and the particle size range of the nano silica is 5-30 nm.
4. The organic-inorganic hybrid wear-resistant coating according to claim 3, characterized in that: the pH range of the nano silica sol is 8-11.
5. The organic-inorganic hybrid wear-resistant coating according to claim 1, characterized in that: the silane coupling agent is methyltrimethoxysilane or methyltriethoxysilane.
6. The organic-inorganic hybrid wear-resistant coating according to claim 1, characterized in that: the organic acid is formic acid or acetic acid.
7. The organic-inorganic hybrid wear-resistant coating according to claim 1, characterized in that: the nano filler is one or more of nano alumina, nano zirconia and silicon carbide.
8. The organic-inorganic hybrid wear-resistant coating according to claim 7, characterized in that: the particle size of the nano filler is less than 5 mu m.
9. The preparation method of the organic-inorganic hybrid wear-resistant coating is characterized by comprising the following specific operation steps:
s1, weighing the raw materials according to the formula in claim 1, sequentially adding the nano silica sol, the silane coupling agent, the organic acid and the hydroxyl-containing silicone oil into a reaction kettle, heating to 40-50 ℃ under the condition of the rotation speed of 300-500rpm, and carrying out heat preservation and dispersion;
s2, adding the polycarbonate modified polyester into the mixture obtained in the step S1 while dispersing under the rotation speed condition of 400-600rpm, heating to 70-80 ℃, and then carrying out heat preservation and dispersion under the rotation speed condition of 800-1200 rpm;
s3, cooling to 25-35 ℃, adding the nano filler while dispersing, and dispersing at the rotation speed of 1000-1500 rpm;
s4, filtering the mixture obtained in the step S3 to obtain the organic-inorganic hybrid wear-resistant coating.
10. The preparation method of the organic-inorganic hybrid wear-resistant coating according to claim 9, wherein the preparation method comprises the following steps: in the step S1, the heat preservation and dispersion time is 3-4 h; in the step S2, the heat preservation dispersion time is 1.5-2 h; in step S3, the dispersion time is 20-30 min; in step S4, the filter bag of 15-25 μm is used for filtration.
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| CN115613348A (en) * | 2022-10-17 | 2023-01-17 | 太原理工大学 | Surface modification method of polyester fiber fabric, modified polyester fiber fabric, preparation method of rubber canvas composite material and application |
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