CN115124920A - Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof - Google Patents
Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof Download PDFInfo
- Publication number
- CN115124920A CN115124920A CN202210935699.5A CN202210935699A CN115124920A CN 115124920 A CN115124920 A CN 115124920A CN 202210935699 A CN202210935699 A CN 202210935699A CN 115124920 A CN115124920 A CN 115124920A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyurethane coating
- castor oil
- repairing
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0871—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a transparent self-repairing anti-contamination polyurethane coating and a preparation method thereof, wherein the coating comprises the following components in parts by weight: 2-4 parts of polysiloxane grafted castor oil polyol, 2-4 parts of polyhexamethylene diisocyanate, 30-50 parts of butanone and 40-60 parts of dimethyl carbonate. The monohydroxy terminated polysiloxane adopted by the invention has no biotoxicity, wide source and low cost; the reaction is exothermic, so the oxalyl chloride is slowly dripped into the reactor to ensure that the reaction is more complete; the monohydroxy terminated polysiloxane and oxalyl chloride can react at normal temperature, other energy sources are not consumed in the reaction process, and the method is environment-friendly; dimethyl carbonate is a poor solvent of PDMS (polydimethylsiloxane) chain forging and is a good solvent of polyol, so that the PDMS chain forging in the polysiloxane grafted castor oil polyol can form nano micelle particles, and the polyurethane coating has the functions of stain resistance and self cleaning.
Description
Technical Field
The invention relates to the technical field of polyurethane high polymer materials, in particular to a transparent self-repairing anti-contamination polyurethane coating and a preparation method thereof.
Background
The antifouling paint is a functional material modified by a low-surface-energy substance, and the modified paint has low surface energy and smooth surface after being cured, so that water-based and oily liquid can easily slide off the surface without leaving marks. Therefore, the coating has wide application prospect in the fields of self-cleaning, anti-doodling, anti-fingerprint and the like.
The preparation method of the existing anti-fouling paint mainly uses a substance containing long-chain fluorine to modify a base coat. However, substances containing long-chain fluorine have biotoxicity and are easy to accumulate in organisms to cause irreversible harm to the environment ecology. In addition, the existing anti-fouling paint is basically prepared from non-renewable raw materials, which is not beneficial to the necessity of sustainable development. Therefore, how to use environmentally friendly low surface energy substances and how to replace non-renewable raw materials with renewable raw materials becomes the focus of research of today.
In view of the above, the present inventors have conducted intensive studies on the above two important problems, and have proposed a transparent self-repairing stain-resistant polyurethane coating and a method for preparing the same.
Disclosure of Invention
In order to solve the technical problems, the invention provides a transparent self-repairing anti-contamination polyurethane coating and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a transparent self-repairing anti-fouling polyurethane coating comprises the following components in parts by weight: 2-4 parts of polysiloxane grafted castor oil polyol (PDMS-g-CO), 2-4 parts of castor oil polyol (CO), 2-4 parts of polyhexamethylene diisocyanate (HDIT), 30-50 parts of butanone and 40-60 parts of dimethyl carbonate.
The invention also provides a preparation method of the transparent self-repairing anti-contamination polyurethane coating, which comprises the following steps:
step S1: slowly dripping 1-2 parts of oxalyl chloride into 1-2 parts of monohydroxy terminated polysiloxane (PDMS-OH) according to the weight part ratio of 0.5-2, stirring for reaction, drying under vacuum condition to remove excessive oxalyl chloride, and dissolving in an organic solvent to obtain a solution A;
step S2: dissolving 1-2 parts by weight of castor oil polyol (CO) in an organic solvent, uniformly stirring, vacuumizing and introducing inert gas for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to parts by weight, 0-4 parts of polysiloxane grafted castor oil polyol (PDMS-g-CO), 0-4 parts of castor oil polyol (CO), 2-4 parts of polyhexamethylene diisocyanate (HDIT), 30-50 parts of butanone and 40-60 parts of dimethyl carbonate are uniformly mixed and coated on a substrate to form a film through thermosetting, so that the self-repairing stain-proof polyurethane coating is obtained.
Further, the stirring time in the step S1 is 6-18h, and the temperature under vacuum condition is 70-90 ℃.
Further, the temperature at the time of stirring in said step S2 is maintained at 45-75 ℃.
Further, the temperature during rotary evaporation in the step S3 is 70-90 ℃, the temperature of the vacuum drying oven is 70-90 ℃, and the time is 0.5-4 h.
Further, the temperature of the thermosetting film in the step S4 is 45-75 ℃.
Further, the organic solvent is any one or a mixture of two or more of the following: ethanol, methanol, N-Dimethylformamide (DMF) or Tetrahydrofuran (THF).
Further, the substrate is glass, wood block or aluminum sheet.
Further, the inert gas is nitrogen.
The beneficial effects of the invention are:
1. the monohydroxy terminated polysiloxane (PDMS-OH) adopted by the invention has no biotoxicity, wide source and low cost. Since the reaction is exothermic, the addition of oxalyl chloride slowly dropwise into the reactor allowed the reaction to proceed more fully. The monohydroxy terminated polysiloxane (PDMS-OH) and the oxalyl chloride can react at normal temperature, other energy sources are not consumed in the reaction process, and the method is environment-friendly. The reaction process is simple, so that the method is suitable for amplifying pilot-plant reactions.
2. The method is carried out in an organic solvent, and the solvent can be removed only under the condition of rotary evaporation after the reaction because of the low boiling point of Tetrahydrofuran (THF).
3. The dimethyl carbonate is a poor solvent of PDMS forging and is a good solvent of polyol, so that the PDMS forging in the polysiloxane grafted castor oil polyol (PDMS-g-CO) can form nano micelle particles. Due to the microphase separation effect in the thermal curing process of polyurethane, the nano micelle layer is dispersed in the coating layer. And because of the low surface energy of PDMS, the micelle can be enriched on the surface of the coating after curing, so that the smooth surface of the coating has the effect of low surface energy. So that the polyurethane coating has the functions of preventing contamination and self-cleaning.
Detailed Description
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: a preparation method of a transparent self-repairing anti-staining polyurethane coating comprises the following steps:
step S1: slowly and dropwise adding 2 parts by weight of oxalyl chloride into 2 parts by weight of monohydroxy-terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 80 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermally cured at the temperature of 45 ℃ to form a film so as to obtain the self-repairing stain-proof polyurethane coating.
Example 2: a preparation method of a transparent self-repairing anti-staining polyurethane coating comprises the following steps:
step S1: slowly dropping 2 parts of oxalyl chloride into 1 part of monohydroxy terminated polysiloxane (PDMS-OH) according to the parts by weight, stirring for 12 hours for reaction, drying at the temperature of 85 ℃ under vacuum condition to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 70 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, removing the organic solvent by rotary evaporation at the temperature of 85 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 85 ℃ for 3.5 hours to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1.5 portions of castor oil polyol (PDMS-g-CO) grafted by polysiloxane, 1.5 portions of castor oil polyol (CO), 2.5 portions of polyhexamethylene diisocyanate (HDIT), 35 portions of butanone and 45 portions of dimethyl carbonate are uniformly mixed and coated on a substrate wood block to be thermoset and filmed at the temperature of 60 ℃ to obtain the self-repairing stain-proof polyurethane coating.
Example 3: a preparation method of a transparent self-repairing anti-staining polyurethane coating comprises the following steps:
step S1: slowly dropping 1 part of oxalyl chloride into 1 part of monohydroxy terminated polysiloxane (PDMS-OH) according to the weight part, stirring for 6 hours for reaction, drying at the temperature of 70 ℃ under vacuum condition to remove excessive oxalyl chloride, and dissolving in 15ml of ethanol to obtain a solution A;
step S2: dissolving 1 part of castor oil polyol (CO) in 20ml of ethanol according to the parts by weight, uniformly stirring, keeping the temperature at 45 ℃ during stirring, vacuumizing, and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 70 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 70 ℃ for 1h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to parts by weight, 2.5 parts of polysiloxane grafted castor oil polyol (PDMS-g-CO), 2.5 parts of castor oil polyol (CO), 1.5 parts of polyhexamethylene diisocyanate (HDIT), 40 parts of butanone and 50 parts of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermally cured at the temperature of 75 ℃ to form a film so as to obtain the self-repairing anti-contamination polyurethane coating.
Example 4: a preparation method of a transparent self-repairing anti-staining polyurethane coating comprises the following steps:
step S1: slowly dripping 1.5 parts of oxalyl chloride into 1 part of monohydroxy terminated polysiloxane (PDMS-OH), stirring for 8 hours for reaction, drying at the temperature of 75 ℃ under vacuum condition to remove excessive oxalyl chloride, and dissolving in 15ml of methanol to obtain a solution A;
step S2: dissolving 1.5 parts by weight of castor oil polyol (CO) in 20ml of methanol, uniformly stirring, keeping the temperature at 50 ℃ during stirring, vacuumizing, and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, removing the organic solvent by rotary evaporation at the temperature of 75 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 75 ℃ for 0.5h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 4 portions of polysiloxane grafted castor oil polyol (PDMS-g-CO), 4 portions of castor oil polyol (CO), 3 portions of polyhexamethylene diisocyanate (HDIT), 45 portions of butanone and 55 portions of dimethyl carbonate are uniformly mixed and coated on a substrate wood block to be thermally cured at the temperature of 70 ℃ to form a film, so that the self-repairing stain-proof polyurethane coating is obtained.
Example 5: a preparation method of a transparent self-repairing anti-staining polyurethane coating comprises the following steps:
step S1: slowly dropping 2 parts of oxalyl chloride into 1 part of monohydroxy-terminated polysiloxane (PDMS-OH) according to the parts by weight, stirring for 10 hours for reaction, drying at the temperature of 90 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of N, N-Dimethylformamide (DMF) to obtain a solution A;
step S2: dissolving 1.8 parts by weight of castor oil polyol (CO) in 20ml of N, N-Dimethylformamide (DMF), uniformly stirring, keeping the temperature of stirring at 75 ℃, vacuumizing, and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 90 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 90 ℃ for 2h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to parts by weight, 2 parts of polysiloxane grafted castor oil polyol (PDMS-g-CO), 2 parts of castor oil polyol (CO), 4 parts of polyhexamethylene diisocyanate (HDIT), 50 parts of butanone and 60 parts of dimethyl carbonate are uniformly mixed, coated on a substrate aluminum sheet and thermally cured at the temperature of 50 ℃ to form a film so as to obtain the self-repairing stain-proof polyurethane coating.
Comparative example 1:
step S1: slowly dripping 2 parts of oxalyl chloride into 2 parts of monohydroxy terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 5 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 80 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 2:
step S1: slowly dripping 2 parts of oxalyl chloride into 0.5 part of monohydroxy-terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing, and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation at the temperature of 80 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 3:
step S1: slowly and dropwise adding 2 parts by weight of oxalyl chloride into 2 parts by weight of monohydroxy-terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation at the temperature of 80 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 1 portion of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 4:
step S1: slowly dripping 2 parts of oxalyl chloride into 2 parts of monohydroxy terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 80 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to parts by weight, 1 part of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 part of castor oil polyol (CO), 8 parts of polyhexamethylene diisocyanate (HDIT), 30 parts of butanone and 40 parts of dimethyl carbonate are uniformly mixed, coated on substrate glass and subjected to thermosetting film forming at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 5:
step S1: slowly and dropwise adding 2 parts by weight of oxalyl chloride into 2 parts by weight of monohydroxy-terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing, and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A to the solution B, rotationally evaporating at 80 ℃ to remove the organic solvent, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 5 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 6:
step S1: slowly dripping 2 parts of oxalyl chloride into 2 parts of monohydroxy terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation at the temperature of 80 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 75 portions of butanone and 40 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 7:
step S1: slowly and dropwise adding 2 parts by weight of oxalyl chloride into 2 parts by weight of monohydroxy-terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation at the temperature of 80 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 15 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
Comparative example 8:
step S1: slowly dripping 2 parts of oxalyl chloride into 2 parts of monohydroxy terminated polysiloxane (PDMS-OH), stirring for 12 hours for reaction, drying at the temperature of 80 ℃ under vacuum to remove excessive oxalyl chloride, and dissolving in 15ml of Tetrahydrofuran (THF) to obtain a solution A;
step S2: dissolving 2 parts by weight of castor oil polyol (CO) in 20ml of Tetrahydrofuran (THF), uniformly stirring, keeping the temperature at 60 ℃ during stirring, vacuumizing and introducing inert gas nitrogen for more than three times to obtain a solution B;
step S3: slowly dropwise adding the solution A into the solution B, removing the organic solvent by rotary evaporation at the temperature of 80 ℃, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven at the temperature of 80 ℃ for 4h to obtain polysiloxane grafted castor oil polyol (PDMS-g-CO);
step S4: according to the weight portion, 1 portion of polysiloxane grafted castor oil polyol (PDMS-g-CO), 1 portion of castor oil polyol (CO), 2 portions of polyhexamethylene diisocyanate (HDIT), 30 portions of butanone and 80 portions of dimethyl carbonate are uniformly mixed and coated on substrate glass to be thermoset and film-formed at the temperature of 45 ℃ to obtain the polyurethane coating.
The polyurethane coatings obtained in examples 1 to 5 and comparative examples 1 to 8 were subjected to surface property tests, and the results of the tests are shown in Table 1 below.
TABLE 1 results of surface Property test of examples 1 to 5 and comparative examples 1 to 8
It can be seen that the polyurethanes obtained in examples 1 to 5 have a large contact angle, a small sliding angle, and a good marker resistance effect. In the comparative example 1, the castor oil polyol (CO) is excessive, because CO contains hydroxyl, the amount of CO is increased, and the hydroxyl which is not reacted can influence the wettability of the coating, so that the coating is too hydrophilic, and the anti-contamination effect is reduced; too little monohydroxy-terminated polysiloxane (PDMS-OH) in comparative example 2 resulted in poor anti-staining effect because of microphase separation during the reaction of PDMS grafted onto polyol with isocyanate, resulting in PDMS enrichment at the coating surface, providing superior slip effect, the less PDMS enrichment, the less anti-staining effect; too little polyhexamethylene diisocyanate (HDIT) in comparative example 3 resulted in poor effect, because polyhexamethylene diisocyanate (HDIT) is a monomer of polyurethane, too little polyhexamethylene diisocyanate (HDIT) resulted in a lower content of polyurethane in the final composition, resulting in an increase in the relative content of hydroxyl groups, resulting in too hydrophilic coating, reducing the stain-proofing effect; excessive amounts of polyhexamethylene diisocyanate (HDIT) in comparative example 4 resulted in increased polyurethane content, which in turn resulted in a decrease in the relative amount of PDMS, affecting phase separation and reducing stain resistance; the butanone and dimethyl carbonate of comparative examples 5-8, either too much or too little, affect the overall solution concentration by acting as diluents in this system, resulting in poor results.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The transparent self-repairing anti-fouling polyurethane coating is characterized by comprising the following components in parts by weight: 2-4 parts of polysiloxane grafted castor oil polyol, 2-4 parts of polyhexamethylene diisocyanate, 30-50 parts of butanone and 40-60 parts of dimethyl carbonate.
2. A preparation method of a transparent self-repairing anti-staining polyurethane coating is characterized by comprising the following steps:
step S1: slowly dripping 1-2 parts of oxalyl chloride into 1-2 parts of monohydroxy terminated polysiloxane according to the parts by weight, stirring for reaction, drying under a vacuum condition to remove redundant oxalyl chloride, and dissolving in an organic solvent to obtain a solution A;
step S2: dissolving 1-2 parts by weight of castor oil polyalcohol in an organic solvent, uniformly stirring, vacuumizing and introducing inert gas for more than three times to obtain a solution B;
step S3: slowly dripping the solution A into the solution B, removing the organic solvent by rotary evaporation, dissolving in acetone, precipitating for several times by using n-hexane, and drying in a vacuum drying oven to obtain polysiloxane grafted castor oil polyol;
step S4: according to the weight portion, 0-4 portions of castor oil polyalcohol grafted by polysiloxane, 0-4 portions of castor oil polyalcohol, 2-4 portions of polyhexamethylene diisocyanate, 30-50 portions of butanone and 40-60 portions of dimethyl carbonate are uniformly mixed and coated on a substrate to be thermally cured to form a film so as to obtain the self-repairing stain-proof polyurethane coating.
3. The method for preparing the transparent self-repairing stain-resistant polyurethane coating material of claim 2, wherein the stirring time in the step S1 is 6-18h, and the temperature under the vacuum condition is 70-90 ℃.
4. The method for preparing the transparent self-repairing stain resistant polyurethane coating of claim 2, wherein the temperature during stirring in step S2 is maintained at 45-75 ℃.
5. The method for preparing the transparent self-repairing stain-resistant polyurethane coating material of claim 2, wherein the temperature during the rotary evaporation in the step S3 is 70-90 ℃, the temperature of the vacuum drying oven is 70-90 ℃, and the time is 0.5-4 h.
6. The method for preparing the transparent self-repairing stain resistant polyurethane coating of claim 2, wherein the thermosetting film forming temperature in the step S4 is 45-75 ℃.
7. The method for preparing the transparent self-repairing stain-resistant polyurethane coating material of claim 2, wherein the organic solvent is any one or a mixture of more than two of the following: ethanol, methanol, N-dimethylformamide or tetrahydrofuran.
8. The method for preparing the transparent self-repairing stain resistant polyurethane coating of claim 2, wherein the substrate is glass, wood or aluminum sheet.
9. The method for preparing the transparent self-repairing stain resistant polyurethane coating of claim 2 wherein the inert gas is nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210935699.5A CN115124920B (en) | 2022-08-05 | 2022-08-05 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210935699.5A CN115124920B (en) | 2022-08-05 | 2022-08-05 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115124920A true CN115124920A (en) | 2022-09-30 |
| CN115124920B CN115124920B (en) | 2023-05-26 |
Family
ID=83386761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210935699.5A Active CN115124920B (en) | 2022-08-05 | 2022-08-05 | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115124920B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| CN105968242A (en) * | 2016-05-30 | 2016-09-28 | 华南理工大学 | Macromolecular hydrogel using polysioxane based polyurethane as cross-linking agent and micelle polymerization preparation method thereof |
| CN110628311A (en) * | 2019-08-26 | 2019-12-31 | 北京化工大学 | Preparation method of polyurethane-based transparent antifouling coating |
| CN111138974A (en) * | 2020-01-06 | 2020-05-12 | 浙江大学衢州研究院 | Hyperbranched silane modified polyurethane composite polysiloxane antifouling paint and preparation method thereof |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
| CN112831012A (en) * | 2021-02-20 | 2021-05-25 | 广州昊毅新材料科技股份有限公司 | Water-based self-repairing coating and coating for TPU invisible car cover |
| CN113214731A (en) * | 2021-04-26 | 2021-08-06 | 中科院广州化灌工程有限公司 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
| CN113292914A (en) * | 2021-05-28 | 2021-08-24 | 华南农业大学 | Plant oil-based photocuring self-cleaning anti-fouling coating and preparation method and application thereof |
| US20210301171A1 (en) * | 2018-08-02 | 2021-09-30 | Akzo Nobel Coatings International B.V. | Coating Composition Comprising Polysiloxane-Modified Polyurethane for Soft-Feel, Stain Resistant Coatings |
| CN114292379A (en) * | 2022-01-14 | 2022-04-08 | 陕西科技大学 | Preparation method of antifouling bio-based polyurethane film |
-
2022
- 2022-08-05 CN CN202210935699.5A patent/CN115124920B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839443A (en) * | 1987-02-04 | 1989-06-13 | Chisso Corporation | Polysiloxane containing hydroxyl groups and a silicone-modified polyurethane using the same |
| CN105968242A (en) * | 2016-05-30 | 2016-09-28 | 华南理工大学 | Macromolecular hydrogel using polysioxane based polyurethane as cross-linking agent and micelle polymerization preparation method thereof |
| US20210301171A1 (en) * | 2018-08-02 | 2021-09-30 | Akzo Nobel Coatings International B.V. | Coating Composition Comprising Polysiloxane-Modified Polyurethane for Soft-Feel, Stain Resistant Coatings |
| CN110628311A (en) * | 2019-08-26 | 2019-12-31 | 北京化工大学 | Preparation method of polyurethane-based transparent antifouling coating |
| CN111138974A (en) * | 2020-01-06 | 2020-05-12 | 浙江大学衢州研究院 | Hyperbranched silane modified polyurethane composite polysiloxane antifouling paint and preparation method thereof |
| CN112029102A (en) * | 2020-08-18 | 2020-12-04 | 集美大学 | Multi-block copolymer, multi-block amphiphilic polymer and preparation method and application thereof |
| CN112831012A (en) * | 2021-02-20 | 2021-05-25 | 广州昊毅新材料科技股份有限公司 | Water-based self-repairing coating and coating for TPU invisible car cover |
| CN113214731A (en) * | 2021-04-26 | 2021-08-06 | 中科院广州化灌工程有限公司 | Durable plant oil-based anti-graffiti easy-to-clean coating and preparation method and application thereof |
| CN113292914A (en) * | 2021-05-28 | 2021-08-24 | 华南农业大学 | Plant oil-based photocuring self-cleaning anti-fouling coating and preparation method and application thereof |
| CN114292379A (en) * | 2022-01-14 | 2022-04-08 | 陕西科技大学 | Preparation method of antifouling bio-based polyurethane film |
Non-Patent Citations (1)
| Title |
|---|
| 方红霞等: "PDMS-MDI-PEG多嵌段共聚物涂层表面微相分离行为研究", 《高分子学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115124920B (en) | 2023-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lei et al. | Transparent omniphobic polyurethane coatings containing partially acetylated β–cyclodextrin as the polyol | |
| CN100503757C (en) | Ultraviolet light solidifying paint containing POSS and its preparation method | |
| Ma et al. | Synthesis and characterization of poly (propylene carbonate) glycol-based waterborne polyurethane with a high solid content | |
| Wei et al. | High-performance bio-based polyurethane antismudge coatings using castor oil-based hyperbranched polyol as superior cross-linkers | |
| US11802204B2 (en) | Thermoset omniphobic compositions with improved barrier properties, related articles, and related methods | |
| Sui et al. | Preparation and properties of polysiloxane modified fluorine-containing waterborne polyurethane emulsion | |
| Sun et al. | Polyurethane covalently modified polydimethylsiloxane (PDMS) coating with increased surface energy and re-coatability | |
| Tan et al. | Preparation and performance of waterborne UV‐curable polyurethane containing long fluorinated side chains | |
| CN109942856B (en) | Hard coating | |
| CN104211899B (en) | Polyacetals modified carboxylic acid nonionic polyurethane aqueous dispersion and preparation method thereof and the application in coating | |
| Wang et al. | Synthesis of UV-curable polyurethane acrylate modified with polyhedral oligomeric silsesquioxane and fluorine for iron cultural relic protection coating | |
| CN108329342B (en) | Organic silicon coupling agent and preparation method and application thereof | |
| Wang et al. | Dynamically oleophobic epoxy coating with surface enriched in silicone | |
| Xu et al. | Preparation and evaluation of degradable polyurethane with low surface energy for marine antifouling coating | |
| Dong et al. | Preparation and characterization of UV-curable waterborne polyurethane using isobornyl acrylate modified via copolymerization | |
| Cui et al. | Fabrication of UV/moisture dual curing coatings based on fluorinated polyoxetanes for anti-fouling applications | |
| Wu et al. | Preparation and properties of autocatalytic biobased waterborne polyol from rosin based epoxy resin | |
| Li et al. | Development of biobased polyol from epoxidized soybean oil for polyurethane anti‐smudge coatings | |
| Tian et al. | Renewable UV-curable polyester methacrylate/cellulose nanocrystals composite resin for wood waterproof coating | |
| CN115124920A (en) | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof | |
| Ren et al. | A Humidity‐Insensitive Waterborne Polyurethane Pressure‐Sensitive Adhesive Modified by Castor Oil and Siloxane | |
| CN106750155A (en) | A kind of preparation method of aqueous polyurethane/fluorine-containing polyphosphazene microspheres composite | |
| Liu et al. | Preparation and characterization of a polydimethylsiloxane‐modified, epoxy‐resin‐based polyol dispersion and its crosslinked films | |
| CN109715750B (en) | Coating composition curable by condensation and/or addition reaction | |
| Honarkar | The effect of different acrylic monomers contents on the properties of waterborne polyurethane/acrylate hybrids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |