A stone coating material having high adhesion and a method for preparing the same
By preparing stone coatings using modified polyurethane oligomers, the problems of insufficient adhesion and antibacterial properties of traditional coatings on stone surfaces have been solved, resulting in stone coatings with high adhesion and antibacterial properties, thus improving the protective effect on stone surfaces.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUSHANG LIANGPIN ENVIRONMENTAL SERVICE (SHANGHAI) CO LTD
- Filing Date
- 2024-11-12
- Publication Date
- 2026-06-19
AI Technical Summary
The existing polyurethane coatings have poor adhesion and antibacterial properties, which are insufficient to meet the requirements of modern stone coatings. Traditional coatings also have problems such as cracking and mildew in the protection of stone surfaces.
Modified polyurethane oligomers are used as the main resin. Modified polyurethane oligomers are prepared through click reaction and nucleophilic addition reaction. Reactive diluents and photoinitiators are added to form stone coatings containing siloxane structures and positively charged quaternary ammonium salts, which enhance the adhesion and antibacterial properties.
It improves the adhesion and antibacterial properties of stone coatings, enhances adhesion to stone surfaces and antibacterial effects, and has good impact resistance and hardness.
Smart Images
Figure CN119490767B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of coating technology, specifically to a stone coating with high adhesion and its preparation method. Background Technology
[0002] Stone is one of the most widely used and oldest building materials in human history. Due to its abundant resources, high compressive strength, durability, wear resistance, and decorative properties, it is widely used in building decoration materials and wall cladding. However, damage from wind, rain, and other factors can lead to cracking, mold, and weathering, making the protection of stone an urgent matter.
[0003] One way to protect stone at present is to coat its surface with a coating. Polyurethane coatings are widely used in wooden furniture, interior decoration and other fields due to their good adhesion and weather resistance. However, with the continuous upgrading of technology, the bonding performance of traditional polyurethane coatings can no longer meet the requirements of stone coatings at present. Therefore, it is necessary to improve the bonding performance of polyurethane coatings.
[0004] For example, the patent with authorization announcement number CN 102140281 B discloses a coating for protecting the back of stone. The coating prepared by this invention is applied to the back of stone and has good adhesion, waterproof and alkali-proof effects, but it does not improve the antibacterial properties of the stone coating. Summary of the Invention
[0005] The purpose of this invention is to provide a stone coating with high adhesion and a method for preparing the same. By preparing a modified polyurethane oligomer, the adhesion, antibacterial properties and mechanical properties of the stone coating are enhanced.
[0006] The technical solution adopted in this invention is:
[0007] A highly adhesive stone coating, wherein the highly adhesive stone coating comprises the following components in parts by weight:
[0008] 20-60 parts by weight of modified polyurethane oligomer, 10-30 parts by weight of polymethyl acrylate, 20-40 parts by weight of reactive diluent, and 2-10 parts by weight of photoinitiator;
[0009] The preparation method of the stone coating is as follows:
[0010] Modified polyurethane oligomer and polymethyl acrylate are stirred and mixed evenly. Then, reactive diluent and photoinitiator are added and stirred to disperse. After standing, stone coating is obtained.
[0011] According to the above technical solution, in a preferred embodiment, the active diluent is one of butyl acrylate and tripropylene glycol diacrylate.
[0012] According to the above technical solution, in a preferred embodiment, the photoinitiator is one of photoinitiator 184 and photoinitiator 1173.
[0013] According to the above technical solution, in a preferred embodiment, the method for preparing the modified polyurethane oligomer is as follows:
[0014] (1) Add diallylamine and γ-mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add azobisisobutyronitrile, and react at 70-80℃ for 20-40 min. After the reaction is completed, rotary evaporate to obtain intermediate 1.
[0015] (2) Intermediate 1 and 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 80-90℃, and reacted for 2-5 hours. After the reaction was completed, the intermediate was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0016] (3) Under a nitrogen atmosphere, intermediate 2 and (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 100-120℃ for 12-24h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0017] (4) Under a nitrogen atmosphere, 1,6-hexamethylene diisocyanate trimer is added to butyl acetate solvent, the temperature is raised to 45-60℃, intermediate 3, hydroquinone polymerization inhibitor and dibutyltin dilaurate are added, the temperature is raised to 65-75℃, and the reaction is carried out for 3-6 hours. After the reaction is completed, the mixture is cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0018] According to the above technical solution, in a preferred case, in step (1), the mass ratio of diallylamine, γ-mercaptopropyltriethoxysilane, and azobisisobutyronitrile is 1:4.8-5.4:0.005-0.01.
[0019] According to the above technical solution, in a preferred case, in step (2), the mass ratio of intermediate 1 to 1,2-epoxy-5-hexene is 1:0.15-0.3.
[0020] According to the above technical solution, in a preferred case, in step (3), the mass ratio of intermediate 2 to (2-chloroethyl)benzene is 1:0.2-0.4.
[0021] According to the above technical solution, in a preferred case, the mass ratio of 1,6-hexamethylene diisocyanate trimer to intermediate 3 in (4) is 1:1.5-2.
[0022] According to the above technical solution, in a preferred case, in step (4), the mass of hydroquinone inhibitor is 0.02-0.06% of the total mass of 1,6-hexamethylene diisocyanate trimer and intermediate 3; and the mass of dibutyltin dilaurate is 0.04-0.08% of the total mass of 1,6-hexamethylene diisocyanate trimer and intermediate 3.
[0023] The beneficial effects of this invention are as follows:
[0024] This invention uses diallylamine and γ-mercaptopropyltriethoxysilane as raw materials. Through a click reaction, intermediate 1 is obtained. Then, it undergoes an epoxy ring-opening reaction with 1,2-epoxy-5-hexene to obtain intermediate 2. The tertiary amine of intermediate 2 is quaternized with (2-chloroethyl)benzene to obtain intermediate 3. Using hydroquinone as a polymerization inhibitor and dibutyltin dilaurate as a catalyst, intermediate 3 and 1,6-hexamethylene diisocyanate trimer are used as the main raw materials. Through a nucleophilic addition reaction, a low molecular weight trifunctional modified polyurethane oligomer is obtained. Using this as the main resin, an active diluent is added and stirred evenly to obtain a stone coating.
[0025] The stone coating prepared by this invention contains a large number of siloxane structures. The silanol groups formed after hydrolysis can undergo a condensation reaction with the hydroxyl groups on the stone surface, thereby increasing the adhesion performance of the coating to the stone. In addition, the urethane bonds contained therein can react with the hydroxyl groups of the stone, further enhancing the adhesion performance between the coating and the stone.
[0026] The stone coating prepared by this invention contains a positively charged quaternary ammonium salt structure, which can be adsorbed onto the surface of negatively charged microorganisms through electrostatic attraction. It binds to the phospholipid bilayer and other negatively charged substances in the cell membrane, disrupting the cell membrane, causing the release of intracellular substances, leading to cell death, and achieving an antibacterial effect. The stone coating prepared by this invention has good adhesion and antibacterial properties. Attached Figure Description
[0027] Figure 1 It is the reaction route for modified polyurethane oligomers. Detailed Implementation
[0028] The high-adhesion stone coating and its preparation method of the present invention will be further described below with reference to some specific embodiments. These specific embodiments are for further detailed explanation of the present invention and are not intended to limit the scope of protection of the present invention.
[0029] Example 1
[0030] (1) According to the weight, 10 parts of diallylamine and 48 parts of γ-mercaptopropyltriethoxysilane were added to toluene solvent, stirred and dispersed, and then 0.05 parts of azobisisobutyronitrile were added. The reaction was carried out at 75°C for 30 min. After the reaction was completed, the mixture was rotary evaporated to obtain intermediate 1.
[0031] (2) By weight, 20 parts of intermediate 1 and 4 parts of 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 80°C, and reacted for 5 hours. After the reaction was completed, the mixture was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0032] (3) Under a nitrogen atmosphere, 20 parts of intermediate 2 and 8 parts of (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 100°C for 24 h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0033] (4) Under a nitrogen atmosphere, 40 parts of 1,6-hexamethylene diisocyanate trimer were added to butyl acetate solvent, the temperature was raised to 45°C, 80 parts of intermediate 3, 0.07 parts of hydroquinone polymerization inhibitor and 0.1 parts of dibutyltin dilaurate were added, the temperature was raised to 70°C and the reaction was carried out for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0034] (5) Mix 20 parts of modified polyurethane oligomer and 30 parts of polymethyl acrylate evenly, then add 40 parts of butyl acrylate reactive diluent and 10 parts of photoinitiator 184, stir and disperse, and let stand to obtain stone coating.
[0035] Example 2
[0036] (1) According to the weight, 10 parts of diallylamine and 50 parts of γ-mercaptopropyltriethoxysilane were added to toluene solvent, stirred and dispersed, and then 0.1 parts of azobisisobutyronitrile were added. The reaction was carried out at 70°C for 40 min. After the reaction was completed, the mixture was rotary evaporated to obtain intermediate 1.
[0037] (2) By weight, 20 parts of intermediate 1 and 5 parts of 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 85°C, and reacted for 2 hours. After the reaction was completed, the mixture was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0038] (3) Under a nitrogen atmosphere, 20 parts of intermediate 2 and 6 parts of (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 110°C for 24 h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0039] (4) Under a nitrogen atmosphere, 40 parts of 1,6-hexamethylene diisocyanate trimer were added to butyl acetate solvent, the temperature was raised to 50°C, 60 parts of intermediate 3, 0.02 parts of hydroquinone polymerization inhibitor and 0.1 parts of dibutyltin dilaurate were added, the temperature was raised to 65°C and the reaction was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0040] (5) Mix 30 parts of modified polyurethane oligomer and 20 parts of polymethyl acrylate evenly, then add 40 parts of tripropylene glycol diacrylate reactive diluent and 10 parts of photoinitiator 184, stir and disperse, and let stand to obtain stone coating.
[0041] Example 3
[0042] (1) According to the weight, 10 parts of diallylamine and 54 parts of γ-mercaptopropyltriethoxysilane were added to toluene solvent, stirred and dispersed, and then 0.05 parts of azobisisobutyronitrile were added. The reaction was carried out at 80℃ for 20 min. After the reaction was completed, the mixture was rotary evaporated to obtain intermediate 1.
[0043] (2) By weight, 20 parts of intermediate 1 and 3 parts of 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 85°C, and reacted for 5 hours. After the reaction was completed, the mixture was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0044] (3) Under a nitrogen atmosphere, 20 parts of intermediate 2 and 8 parts of (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 100°C for 24 h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0045] (4) Under a nitrogen atmosphere, 40 parts of 1,6-hexamethylene diisocyanate trimer were added to butyl acetate solvent, the temperature was raised to 60°C, 70 parts of intermediate 3, 0.05 parts of hydroquinone polymerization inhibitor and 0.04 parts of dibutyltin dilaurate were added, the temperature was raised to 75°C and the reaction was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0046] (5) Mix 40 parts of modified polyurethane oligomer and 10 parts of polymethyl acrylate evenly, then add 40 parts of butyl acrylate reactive diluent and 10 parts of photoinitiator 1173, stir and disperse, and let stand to obtain stone coating.
[0047] Example 4
[0048] (1) According to the weight, 10 parts of diallylamine and 52 parts of γ-mercaptopropyltriethoxysilane were added to toluene solvent, stirred and dispersed, and then 0.05 parts of azobisisobutyronitrile were added. The reaction was carried out at 75°C for 30 min. After the reaction was completed, the mixture was rotary evaporated to obtain intermediate 1.
[0049] (2) By weight, 20 parts of intermediate 1 and 4 parts of 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 80°C, and reacted for 5 hours. After the reaction was completed, the mixture was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0050] (3) Under a nitrogen atmosphere, 20 parts of intermediate 2 and 6 parts of (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 110°C for 24 h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0051] (4) Under a nitrogen atmosphere, 40 parts of 1,6-hexamethylene diisocyanate trimer were added to butyl acetate solvent, the temperature was raised to 50°C, 70 parts of intermediate 3, 0.05 parts of hydroquinone polymerization inhibitor and 0.1 parts of dibutyltin dilaurate were added, the temperature was raised to 65°C and the reaction was carried out for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0052] (5) Mix 50 parts of modified polyurethane oligomer and 20 parts of polymethyl acrylate evenly, then add 20 parts of tripropylene glycol diacrylate reactive diluent and 10 parts of photoinitiator 184 to the mixture and stir to disperse. Let stand to obtain stone coating.
[0053] Example 5
[0054] (1) According to the weight, 10 parts of diallylamine and 48 parts of γ-mercaptopropyltriethoxysilane were added to toluene solvent, stirred and dispersed, and then 0.1 parts of azobisisobutyronitrile were added. The reaction was carried out at 75°C for 30 min. After the reaction was completed, the mixture was rotary evaporated to obtain intermediate 1.
[0055] (2) By weight, 20 parts of intermediate 1 and 6 parts of 1,2-epoxy-5-hexene were added to toluene solvent, stirred and dispersed, heated to 90°C, and reacted for 2 hours. After the reaction was completed, the mixture was distilled under reduced pressure and recrystallized to obtain intermediate 2.
[0056] (3) Under a nitrogen atmosphere, 20 parts of intermediate 2 and 4 parts of (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 120°C for 12 h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3.
[0057] (4) Under a nitrogen atmosphere, 40 parts of 1,6-hexamethylene diisocyanate trimer were added to butyl acetate solvent, the temperature was raised to 50°C, 70 parts of intermediate 3, 0.05 parts of hydroquinone polymerization inhibitor and 0.05 parts of dibutyltin dilaurate were added, the temperature was raised to 70°C and the reaction was carried out for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain modified polyurethane oligomer.
[0058] (5) Mix 60 parts of modified polyurethane oligomer and 18 parts of polymethyl acrylate evenly, then add 20 parts of tripropylene glycol diacrylate reactive diluent and 2 parts of photoinitiator 184, stir and disperse, and let stand to obtain stone coating.
[0059] Apply the stone coating to a clean stone surface using a roller coating method, let it sit for 5 minutes, and then place it under a light curing machine to cure it into a film. The curing conditions are a 2KW high-pressure lamp with a power density of 100W / cm and a curing time of 10s.
[0060] The adhesion of the coating was determined in accordance with GB / T1720-1979.
[0061] The coating hardness was tested in accordance with GB / T6739-2006.
[0062] The impact resistance of the coating was tested in accordance with GB / T1732-1993.
[0063] Table 1:
[0064]
[0065]
[0066] The higher the adhesion rating, the better the bonding performance. As shown in the table, the coating prepared by this invention has good bonding performance. The table also shows that with the increase of modified polyurethane oligomers, the double bond content increases, the number of active groups increases, the crosslinking density increases, and its impact resistance increases. Furthermore, with the increase of rigid groups such as phenyl and six-membered rings in the polyurethane coating, its hardness increases.
[0067] According to HG / T3950-2007, the tested microorganisms were Escherichia coli and Staphylococcus aureus.
[0068] Table 2:
[0069]
[0070] As shown in the table, the stone coating prepared by this invention has good antibacterial properties, with an antibacterial rate of up to 99.9%.
[0071] For anyone skilled in the art, many possible variations and modifications can be made to the technical solutions of this invention, or equivalent embodiments can be modified based on the disclosed technical content, without departing from the scope of the technical solutions of this invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this invention without departing from the content of the technical solutions of this invention should still fall within the protection scope of the technical solutions of this invention.
Claims
1. A stone coating having high adhesion, characterized by, The high-adhesion stone coating is composed of the following components in parts by weight: 20-60 parts by weight of modified polyurethane oligomer, 10-30 parts by weight of polymethyl acrylate, 20-40 parts by weight of reactive diluent, and 2-10 parts by weight of photoinitiator; The preparation method of the stone coating is as follows: Modified polyurethane oligomer and polymethyl acrylate are stirred and mixed evenly. Then, reactive diluent and photoinitiator are added and stirred to disperse. After standing, stone coating is obtained. The preparation method of the modified polyurethane oligomer: (1) Add diallylamine and γ-mercaptopropyltriethoxysilane to toluene solvent, stir and disperse, then add azobisisobutyronitrile, and react at 70-80℃ for 20-40 min. After the reaction is completed, rotary evaporate to obtain intermediate 1. (2) Add intermediate 1 and 1,2-epoxy-5-hexene to toluene solvent, stir and disperse, heat to 80-90℃, react for 2-5 h, after the reaction is completed, distill under reduced pressure and recrystallize to obtain intermediate 2; (3) Under a nitrogen atmosphere, intermediate 2 and (2-chloroethyl)benzene were added to an ethanol solvent, stirred and mixed evenly, and reacted at 100-120℃ for 12-24h. After the reaction was completed, the mixture was recrystallized and dried to obtain intermediate 3. (4) Under a nitrogen atmosphere, 1,6-hexamethylene diisocyanate trimer is added to butyl acetate solvent, the temperature is raised to 45-60℃, intermediate 3, hydroquinone polymerization inhibitor and dibutyltin dilaurate are added, the temperature is raised to 65-75℃, and the reaction is carried out for 3-6 hours. After the reaction is completed, the mixture is cooled to room temperature and discharged to obtain modified polyurethane oligomer.
2. The stone paint having high adhesion according to claim 1, characterized by, The reactive diluent is one of butyl acrylate and tripropylene glycol diacrylate.
3. The stone paint having high adhesion according to claim 1, characterized by, The photoinitiator is one of photoinitiator 184 and photoinitiator 1173.
4. The stone paint having high adhesion according to claim 1, characterized by, In (1), the mass ratio of diallylamine, γ-mercaptopropyltriethoxysilane, and azobisisobutyronitrile is 1:4.8-5.4:0.005-0.
01.
5. The stone paint having high adhesion according to claim 1, characterized by, In (2), the mass ratio of intermediate 1 to 1,2-epoxy-5-hexene is 1:0.15-0.
3.
6. The stone paint having high adhesion according to claim 1, characterized by, In (3), the mass ratio of intermediate 2 to (2-chloroethyl)benzene is 1:0.2-0.
4.
7. The stone paint having high adhesion according to claim 1, characterized by, In (4), the mass ratio of 1,6-hexamethylene diisocyanate trimer to intermediate 3 is 1:1.5-2.
8. The stone paint having high adhesion according to claim 1, characterized by, In (4), the mass of hydroquinone inhibitor is 0.02-0.06% of the total mass of 1,6-hexamethylene diisocyanate trimer and intermediate 3; the mass of dibutyltin dilaurate is 0.04-0.08% of the total mass of 1,6-hexamethylene diisocyanate trimer and intermediate 3.