CN114716898B - Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating - Google Patents
Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating Download PDFInfo
- Publication number
- CN114716898B CN114716898B CN202210394285.6A CN202210394285A CN114716898B CN 114716898 B CN114716898 B CN 114716898B CN 202210394285 A CN202210394285 A CN 202210394285A CN 114716898 B CN114716898 B CN 114716898B
- Authority
- CN
- China
- Prior art keywords
- parts
- modified
- polyurethane
- acrylate
- modified acrylate
- 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.)
- Active
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
- C09D175/06—Polyurethanes from polyesters
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to an interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating which comprises the following raw materials in parts by weight: 75-85 parts of polyurethane modified acrylate emulsion, 0.3-0.8 part of defoaming agent, 0.4-1 part of flatting agent, 1-4 parts of thixotropic agent, 0.5-2.5 parts of wetting dispersant, 5-10 parts of strippable auxiliary agent and 1-10 parts of deionized water; the polyurethane modified acrylate emulsion comprises the following raw materials: 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 0-2 parts of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water. The coating disclosed by the invention is excellent in weather resistance, high in strength, high in elongation at break, low in film forming temperature, good in flexibility, low in requirement on production equipment, self-cleaning and applicable to temporary protection of large-scale mechanical equipment.
Description
Technical Field
The invention relates to an interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating, and belongs to the field of coatings.
Background
With the development of the manufacturing industry of mechanical equipment in China, particularly, the time interval from production to handover of large-scale mechanical equipment is long, and the large-scale mechanical equipment is generally placed at an idle position outside a workshop. The paint film of mechanical equipment is damaged by rain corrosion, ultraviolet irradiation and external force scratching, and meanwhile, dust in air adheres to the surface of the paint film and is difficult to clean, so that the handover process is difficult to be smooth. The plastic film is used for covering, so that the device is difficult to protect comprehensively, and particularly in eastern coastal areas with strong ultraviolet rays and high humidity. The currently common temporary protective strippable coatings are oily most commonly, but have high VOC content, strong odor and dangerous transportation process. With the higher and higher requirements of national environmental protection, the application of the water-based strippable coating is more and more extensive. Aqueous peelable emulsions are common in acrylate emulsions and polyurethane emulsions. The acrylate peelable paint has excellent weather resistance, but has the defects of low strength, high peel strength, low-temperature cracking and the like, and the application of the acrylate peelable paint is limited. The polyurethane strippable coating has the advantages of high strength, high elongation at break, low film-forming temperature, good flexibility, poor weather resistance and higher requirements on production equipment, and does not meet the environmental protection requirement because an organic solvent is required to be added for dilution in production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating which is a single-component solvent-free polyurethane modified acrylate strippable coating, has excellent weather resistance, high strength, high elongation at break, low film forming temperature, good flexibility and low requirement on production equipment, can self-clean and is used for temporary protection of large mechanical equipment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
technical subject 1
An interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating comprises the following raw materials in parts by weight: 75-85 parts of polyurethane modified acrylate emulsion, 0.3-0.8 part of defoaming agent, 0.4-1 part of flatting agent, 1-4 parts of thixotropic agent, 0.5-2.5 parts of wetting dispersant, 5-10 parts of strippable auxiliary agent and 1-10 parts of deionized water;
the polyurethane modified acrylate emulsion comprises the following raw materials: 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 0-2 parts of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water.
As a preferred embodiment of the present invention, the emulsifier may be selected from one of OP-10, Adeca SR-10, Adeca ER-10, and Amersham COPS-1, which is a new material science and technology Co.Ltd, and preferably, Adeca SR-10 and Adeca ER-10 are used in combination.
In a preferred embodiment of the invention, the strippable auxiliary is selected from one of Malus spectabilis chemical JF-9565, Shanghai Hui research New Material company HY-3667 and Zhan Xin Xi ADDITOL-XL6568, preferably Zhan Xin Xi ADDITOL-XL 6568.
As a preferred embodiment of the invention, the antifoaming agent is selected from one of BYK-024, Digao Foamex 810, Tego-825, HY-825, preferably HY-825.
As a preferred embodiment of the invention, the leveling agent is one selected from KMT-5510, BYK-3560, ECO-3880 and HY-381, and HY-381 is preferred.
As a preferred embodiment of the present invention, the thixotropic agent is selected from one of ECO-6000, BYK-420, Anjeka4420, preferably Anjeka 4420.
As a preferred embodiment of the invention, the hydrophilic organic silicon modified polyurethane prepolymer comprises the following raw materials in parts by weight: 30-40 parts of polyester diol, 0-10 parts of polycaprolactone diol, 0-10 parts of polypropylene oxide ether diol, 15-20 parts of hexamethylene diisocyanate, 15-20 parts of isophorone diisocyanate, 6-10 parts of a hydrophilic chain extender, 1-3 parts of trimethylolpropane, 5-12 parts of hydroxypropyl silicone oil and 0.1-0.3 part of phenylmercuric acetate.
As a preferred embodiment of the invention, the polyurethane modified acrylate emulsion comprises the following raw materials in parts by weight: 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 1 part of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water.
As a preferred embodiment of the invention, the preparation method of the hydrophilic organic silicon modified polyurethane prepolymer comprises the steps of sequentially putting a self-hydrophilic chain extender, trimethylolpropane, hexamethylene diisocyanate, isophorone diisocyanate, phenylmercuric acetate, polyester diol, polycaprolactone diol, polypropylene oxide ether diol and hydroxypropyl silicone oil into a reaction kettle, reacting for 3 hours at 80-85 ℃, and stopping heating after the content of isocyanate is determined to reach a theoretical value, so as to obtain the hydrophilic organic silicon modified polyurethane prepolymer.
As a preferred embodiment of the invention, the raw materials of the polyester diol are prepared from 14.8 parts by weight of adipic acid, 22 parts by weight of hexanediol, 16 parts by weight of terephthalic acid, 10-15 parts by weight of 1, 8-octanediol, 15-20 parts by weight of 1, 2-octanediol and 14.2 parts by weight of phthalic anhydride.
As a preferred embodiment of the present invention, the method for preparing the polyester diol comprises the steps of:
adding adipic acid, hexanediol, terephthalic acid, 1, 8-octanediol, 1, 2-octanediol and phthalic anhydride into a four-opening bottle with vacuumizing, a bayonet condenser and nitrogen protection, gradually heating to 90-110 ℃, reacting for 20min, then gradually heating to 150-160 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the column head temperature to be lower than 98 ℃, reacting for 5-6h, and stopping heating after the acid value is determined to reach below 3mgKOH/g to obtain the polyester diol.
As a preferred embodiment of the present invention, the preparation method of the hydrophilic chain extender comprises the steps of:
the phthalic anhydride is added into the triethanolamine in 4 batches at 45 ℃, the temperature is controlled not to exceed 50 ℃, and then the reaction is continued for 2 hours at 60 ℃. And stopping heating to obtain the hydrophilic chain extender.
As a preferred embodiment of the present invention, the method for preparing the modified hexamethylenediamine comprises the steps of:
preparing 35-40 parts of butyl acrylate, 25-28 parts of methyl acrylate and 30-40 parts of hexamethylene diamine according to parts by weight;
adding hexamethylene diamine into a reaction kettle, dropwise adding butyl acrylate into the reaction kettle by using a constant-pressure dropping funnel, keeping the temperature below 35 ℃, and reacting for 2 hours; then dropwise adding methyl acrylate, keeping the temperature below 35 ℃, and reacting for 2 hours; then the reaction is continued for 3h at 90 ℃, and the heating is stopped, thus obtaining the modified hexamethylene diamine.
As a preferred embodiment of the present invention, the preparation method of the polyurethane modified acrylate emulsion comprises the following steps:
A. preparing 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 0-2 parts of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water for later use;
B. mixing the hydrophilic organic silicon modified polyurethane prepolymer, butyl methacrylate, isooctyl acrylate, an emulsifier SR-10, an emulsifier ER-10 and hexanediol diacrylate, and stirring at the stirring speed of 100-;
C. setting the rotation speed to be 800-1000r/min, adding deionized water into the primary mixed liquid for emulsification for 20min, then slowly adding the modified hexamethylene diamine and the hexamethylene diamine, continuously dispersing for 20min after dripping for 3-5min, and adding ammonium persulfate and sodium bicarbonate to obtain a pre-emulsion;
D. adding the pre-emulsion into a reaction kettle with nitrogen protection, mechanical stirring and a spherical condenser pipe, gradually heating to 80 ℃ at 70 ℃ at the speed of 5-10 ℃/min, reacting for 3 hours, continuing to react for 2 hours at 90 ℃, and stopping heating to obtain the waterborne interpenetrating network structure polyurethane modified acrylate emulsion.
Subject matter two
A preparation method of an interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating comprises the following steps: stirring the polyurethane modified acrylate emulsion, the defoaming agent and the leveling agent for 10-15min at a stirring speed of 500-.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1. the gel fraction of the waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating provided by the invention is below 0.5%, the tensile strength is above 7MPa, the elongation at break is more than 400%, and the surface tension is less than 26 mN/m.
2. The invention utilizes the 1, 2-octanediol and the 1, 8-octanediol to be matched for use, the 1, 2-octanediol can play a certain internal plasticizing effect, the 1, 8-octanediol has good flexibility for improving the mechanical property, and the hard section aggregation of carbamate in polyurethane is reduced, so that the surface tension and the peel strength can be reduced and the elongation at break and the tensile strength can be improved by matching for use.
3. The self-made polyester diol molecular chain contains the side group with lower polarity, so that the interaction between the temporary protective coating and the base material can be reduced, and the peel strength between the peelable coating and the base material is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following description of the present invention is given for clarity and completeness.
Each of the materials in the formulations of the present invention are commercially available. The hydroxypropyl silicone oil is HY-2510 produced by Shanghai Hui Zhenhui new material Co., Ltd, the emulsifier is Japanese adico SR-10 and ER-10, the strippable assistant is Zhanxin ADDITOL-XL6568, the defoamer is HY-825 produced by Shanghai Hui Zhenhui new material Co., Ltd, the flatting agent is HY-381 produced by Shanghai Hui Zhenhui new material Co., Ltd, the color paste is basf Dispers Blue 6900, the thixotropic agent is Anjeka4420, the polycaprolactone diol is polycaprolactone diol 1000, and the polypropylene oxide ether diol is polypropylene oxide ether diol DL-1000D.
The modified hexamethylenediamine in the following examples was prepared from the following starting materials:
| acrylic acid butyl ester | 39 portions of |
| Acrylic acid methyl ester | 26 portions of |
| Hexamethylene diamine | 35 portions of |
The modified hexamethylene diamine is prepared by the following method:
hexamethylenediamine is added into a four-mouth bottle with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, and butyl acrylate is added into the four-mouth bottle drop by drop. The temperature is kept below 35 ℃ and the reaction is carried out for 2 h. And then adding methyl acrylate dropwise, keeping the temperature below 35 ℃ and reacting for 2 h. After the addition is finished, the temperature is set to be 90 ℃ and the reaction is continued for 3 h. Stopping heating to obtain the modified hexamethylene diamine.
The hydrophilic chain extender is prepared from the following raw materials:
| phthalic anhydride | 14.8 parts of |
| Triethanolamine | 22 portions of |
The hydrophilic chain extender is prepared by the following method:
adding triethanolamine into a four-mouth bottle with a mechanical stirrer and a thermometer, setting the temperature at 45 ℃, averagely adding phthalic anhydride in 4 batches, and after the reaction is finished, setting the temperature at 60 ℃ and continuing to react for 2 hours. And stopping heating to obtain the hydrophilic chain extender.
The self-made polyester diol in the following examples is prepared from the following raw materials:
| adipic acid | 14.8 parts of |
| Hexanediol | 22 portions of |
| Terephthalic acid (TPA) | 16 portions of |
| 1, 8-octanediol | 13 portions of |
| 1, 2-octanediol | 16 portions of |
| Phthalic anhydride | 14.2 parts of |
The self-made polyester diol is prepared by the following method:
adding 14.8 parts of adipic acid, 22 parts of hexanediol, 16 parts of terephthalic acid, 13 parts of 1, 8-octanediol, 16 parts of 1, 2-octanediol and 14.2 parts of phthalic anhydride into a four-opening bottle with vacuumizing, a bayonet condenser and nitrogen protection, gradually heating to 90-110 ℃, reacting for 20min, gradually heating to 150-160 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the column head temperature to be lower than 98 ℃, reacting for 5-6h, and stopping heating after the acid value is measured to be below 3mgKOH/g to obtain the self-made polyester diol.
In the following examples, the modified hexamethylenediamine and/or hexamethylenediamine is added slowly, i.e., dropwise, over 3-5 min.
Example 1
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 40 parts of self-made polyester diol, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate into a four-mouth bottle in sequence, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group reaches a theoretical value to obtain a hydrophilic organic silicon modified polyurethane prepolymer No. 1.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 1, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and at a speed of 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Example 2
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
In the same manner as in example 1, hydrophilic silicone-modified polyurethane prepolymer # 1 was obtained.
Step 2 polyurethane modified acrylate emulsion
32 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 1, 7 parts of butyl methacrylate, 8 parts of isooctyl acrylate, 2 parts of SR-10, 2.2 parts of ER-10 and 2 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature to be 70 ℃, gradually heating to 80 ℃ at the speed of 5 ℃/min, reacting for 2 hours, setting the temperature to be 90 ℃, and continuing to react for 2 hours. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 80 parts by weight of polyurethane modified acrylate emulsion, 0.5 part by weight of defoaming agent and 0.5 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 3 parts by weight of color paste, 4 parts by weight of thixotropic agent, 8 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 3.7 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Example 3
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
In the same manner as in example 1, hydrophilic silicone-modified polyurethane prepolymer # 1 was obtained.
Step 2 polyurethane modified acrylate emulsion
40 parts of hydrophilic organic silicon modified polyurethane prepolymer 1#, 2 parts of butyl methacrylate, 6.5 parts of isooctyl acrylate, 1 part of SR-10, 1 part of ER-10 and 1 part of HDDA are added into a high-speed dispersion kettle, and the mixture is uniformly stirred at the set stirring speed of 100 and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 75 parts by weight of polyurethane modified acrylate emulsion, 0.8 part by weight of defoaming agent and 0.4 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 5 parts by weight of color paste, 2 parts by weight of thixotropic agent, 6.5 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 10 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Example 4
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 37.7 parts of self-made polyester diol, 8 parts of self-made hydrophilic chain extender, 2 parts of trimethylolpropane, 20 parts of HDI, 20 parts of IPDI, 12 parts of monohydroxypropyl silicone oil and 0.3 part of phenylmercuric acetate into a four-mouth bottle in sequence, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group reaches a theoretical value to obtain a hydrophilic organic silicon modified polyurethane prepolymer No. 2.
Step 2 polyurethane modified acrylate emulsion
32 parts of hydrophilic organic silicon modified polyurethane prepolymer 2#, 7 parts of butyl methacrylate, 8 parts of isooctyl acrylate, 2 parts of SR-10, 2.2 parts of ER-10 and 2 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Example 5
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
In the same manner as in example 4, hydrophilic silicone-modified polyurethane prepolymer # 2 was obtained.
Step 2 polyurethane modified acrylate emulsion
40 parts of hydrophilic organic silicon modified polyurethane prepolymer 2#, 2 parts of butyl methacrylate, 6.5 parts of isooctyl acrylate, 1 part of SR-10, 1 part of ER-10 and 1 part of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 80 parts by weight of polyurethane modified acrylate emulsion, 0.5 part by weight of defoaming agent and 0.5 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 3 parts by weight of color paste, 4 parts by weight of thixotropic agent, 8 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 3.7 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Example 6
Step 1 hydrophilic organic silicon modified polyurethane prepolymer No. 2
In the same manner as in example 4, 2# hydrophilic silicone-modified polyurethane prepolymer.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 2, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. And stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating
Adding 75 parts by weight of polyurethane modified acrylate emulsion, 0.8 part by weight of defoaming agent and 0.4 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 5 parts by weight of color paste, 2 parts by weight of thixotropic agent, 6.5 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 10 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Example 7
Step 1. hydrophilic organic silicon modified polyurethane prepolymer
Sequentially adding 30 parts of self-made polyester diol, 10 parts of polycaprolactone diol 1000, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate into a four-mouth bottle, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the measured isocyanic acid radical reaches a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 3.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 3, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and at a speed of 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of modified hexamethylene diamine, continuing to disperse for 20min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Example 8
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Sequentially adding 30 parts of self-made polyester diol, 10 parts of polypropylene oxide ether diol DL-1000D, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate into a four-mouth bottle, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, measuring the content of isocyanic acid radical and stopping heating after the content reaches a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 4
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 4, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and at a speed of 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. And stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Example 9
Step 1. hydrophilic organic silicon modified polyurethane prepolymer
Sequentially adding 30 parts of self-made polyester diol, 10 parts of polycaprolactone diol 1000, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate into a four-mouth bottle, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group reaches a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 3.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 3, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and at a speed of 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Example 10
Step 1. hydrophilic organic silicon modified polyurethane prepolymer
Adding 30 parts of self-made polyester diol, 10 parts of polycaprolactone diol 1000, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate into a four-mouth bottle in sequence, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group is measured to reach a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 3.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 3, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and at a speed of 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of hexamethylene diamine, continuing to disperse for 10min, adding 1 part of hexamethylene diamine for dispersion for 10min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Test example 1
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
In the same manner as in example 4, hydrophilic silicone-modified polyurethane prepolymer No. 2 was obtained
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 2, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotation speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating
Adding 75 parts by weight of polyurethane modified acrylate emulsion, 0.8 part by weight of defoaming agent and 0.4 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 5 parts by weight of color paste, 2 parts by weight of thixotropic agent, 6.5 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 10 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Test example 2
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 37.7 parts of polycaprolactone diol 1000, 8 parts of self-made hydrophilic chain extender, 2 parts of trimethylolpropane, 20 parts of HDI, 20 parts of IPDI, 12 parts of monohydroxypropyl silicone oil and 0.3 part of phenylmercuric acetate into a four-mouth bottle in sequence, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, measuring the content of isocyanic acid radical, and stopping heating to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 3.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 2, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of hexamethylene diamine, continuing to disperse for 20min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature to be 70 ℃, gradually heating to 80 ℃ at the speed of 5 ℃/min, reacting for 2 hours, setting the temperature to be 90 ℃, and continuing to react for 2 hours. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 75 parts of polyurethane modified acrylate emulsion, 0.8 part of defoaming agent and 0.4 part of flatting agent by weight, stirring for 10-15 minutes at 800 revolutions per minute, adding 5 parts of color paste, 2 parts of thixotropic agent, 6.5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 10 parts of deionized water at 300 revolutions per minute, stirring for 20-35 minutes, and discharging.
Test example 3
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 37.7 parts of polypropylene oxide ether dihydric alcohol DL-1000D, 8 parts of self-made hydrophilic chain extender, 2 parts of trimethylolpropane, 20 parts of HDI, 20 parts of IPDI, 12 parts of monohydroxypropyl silicone oil and 0.3 part of phenylmercuric acetate into a four-mouth bottle in sequence, and reacting for 2 hours at 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group reaches a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer No. 3.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer No. 2, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of hexamethylene diamine, continuing to disperse for 20min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 75 parts by weight of polyurethane modified acrylate emulsion, 0.8 part by weight of defoaming agent and 0.4 part by weight of flatting agent, stirring for 10-15 minutes at 800 revolutions per minute, adding 5 parts by weight of color paste, 2 parts by weight of thixotropic agent, 6.5 parts by weight of stripping aid, 0.2 part by weight of wetting dispersant, 0.1 part by weight of mildew preventive and 10 parts by weight of deionized water, stirring for 20-35 minutes at 600 revolutions per minute, and discharging.
Comparative example 1
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 14.8 parts of adipic acid, 22 parts of hexanediol, 16 parts of terephthalic acid, 29 parts of 1, 2-octanediol and 14.2 parts of phthalic anhydride into a four-mouth bottle with a vacuumizing, bayonet-type condensing tube and nitrogen protection, gradually heating to 90 ℃, reacting for 20min, gradually heating to 150 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the temperature of a column head to be lower than 98 ℃, reacting for 5h, and stopping heating after the acid value is determined to be less than 3 to obtain the self-made polyester dihydric alcohol.
40 parts of self-made polyester diol, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate are added into a four-mouth bottle in sequence and reacted for 2 hours at the temperature of 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, and stopping heating after the content of the isocyanate group is measured to reach a theoretical value to obtain the hydrophilic organic silicon modified polyurethane prepolymer D1 #.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer D1#, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of modified hexamethylene diamine, continuing to disperse for 20min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature to be 70 ℃, gradually heating to 80 ℃ at the speed of 5 ℃/min, reacting for 2 hours, setting the temperature to be 90 ℃, and continuing to react for 2 hours. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Comparative example 2
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 14.8 parts of adipic acid, 22 parts of hexanediol, 16 parts of terephthalic acid, 29 parts of 1, 8-octanediol and 14.2 parts of phthalic anhydride into a four-mouth bottle with a vacuumizing, bayonet-type condensing tube and nitrogen protection, gradually heating to 90 ℃, reacting for 20min, gradually heating to 150 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the temperature of a column head to be lower than 98 ℃, reacting for 5h, and stopping heating after the acid value is determined to be less than 3 to obtain the self-made polyester dihydric alcohol.
40 parts of self-made polyester diol, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate are added into a four-mouth bottle in sequence and reacted for 2 hours at the temperature of 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, measuring the content of isocyanate group to reach a theoretical value, and stopping heating to obtain the hydrophilic organic silicon modified polyurethane prepolymer D2 #.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer D2#, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at a stirring speed of 100 plus materials and 200 r/min. Setting the rotation speed to be 800-1000r/min, adding 50 parts of water for emulsification for 20min, slowly adding 5 parts of modified hexamethylene diamine, continuing to disperse for 20min, and adding 0.6 part of ammonium persulfate and 0.4 part of sodium bicarbonate to obtain the pre-emulsion. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature to be 70 ℃, gradually heating to 80 ℃ at the speed of 5 ℃/min, reacting for 2 hours, setting the temperature to be 90 ℃, and continuing to react for 2 hours. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
Comparative example 3
Step 1 hydrophilic organic silicon modified polyurethane prepolymer
Adding 14.8 parts of adipic acid, 22 parts of hexanediol, 16 parts of terephthalic acid and 14.2 parts of phthalic anhydride into a four-mouth bottle with vacuumizing, a bayonet condenser and nitrogen protection, gradually heating to 90 ℃, reacting for 20min, gradually heating to 150 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the temperature of a column head to be lower than 98 ℃, reacting for 5h, and stopping heating after the acid value is measured to be below 3 to obtain the self-made polyester diol.
40 parts of self-made polyester diol, 10 parts of self-made hydrophilic chain extender, 3 parts of trimethylolpropane, 15 parts of HDI (hexamethylene diisocyanate), 20 parts of IPDI (isophorone diisocyanate), 11.8 parts of dihydroxypropyl silicone oil and 0.2 part of phenylmercuric acetate are added into a four-mouth bottle in sequence and reacted for 2 hours at the temperature of 60 ℃. Setting the temperature of 80-85 ℃ for reaction for 3h, measuring the content of isocyanate group to reach a theoretical value, and stopping heating to obtain the hydrophilic organic silicon modified polyurethane prepolymer D3 #.
Step 2 polyurethane modified acrylate emulsion
20 parts of hydrophilic organic silicon modified polyurethane prepolymer D3#, 10 parts of butyl methacrylate, 5 parts of isooctyl acrylate, 3 parts of SR-10, 3 parts of ER-10 and 3 parts of HDDA (hexanediol diacrylate) are added into a high-speed dispersion kettle, and the mixture is stirred uniformly at the stirring speed of 100 plus materials and 200 r/min. Setting the rotating speed at 800-. Adding the pre-emulsion into a four-mouth bottle with nitrogen protection, mechanical stirring and a spherical condenser tube, setting the temperature at 70 ℃, gradually heating to 80 ℃ at 5 ℃/min for reaction for 2h, and setting the temperature at 90 ℃ for continuous reaction for 2 h. Stopping heating to obtain the polyurethane modified acrylate emulsion.
Step 3, water-based polyurethane modified acrylate equipment temporary protective coating with interpenetrating network structure
Adding 85 parts of polyurethane modified acrylate emulsion, 0.3 part of defoaming agent and 1 part of flatting agent according to the parts by weight, stirring for 10-15 minutes at 800 revolutions/minute in 500-fold mortar, adding 2 parts of color paste, 1 part of thixotropic agent, 5 parts of stripping aid, 0.2 part of wetting dispersant, 0.1 part of mildew preventive and 5.4 parts of deionized water, stirring for 20-35 minutes at 600 revolutions/minute, and discharging.
The waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating prepared in the examples 1-10, the experimental examples 1-3 and the comparative examples 1-3 is subjected to performance test, the peel strength is tested according to GB/T2790-1995, the tensile strength and the elongation at break are tested according to GB/T16777-2008, and the test results are shown in the following table in GB/T1863-2009:
TABLE 1 Performance testing of protective coatings
| Examples | Gel fraction (%) | Peel strength (N/mm) | Tensile Strength (MPa) | Elongation at Break (%) | Surface tension (mN/m) | Ultraviolet aging (500 h) |
| Example 1 | 0.32 | 1.2 | 7.3 | 430 | 25.6 | No cracking and stickiness |
| Example 2 | 0.35 | 1.2 | 7.1 | 460 | 25.5 | No cracking and stickiness |
| Example 3 | 0.31 | 1.2 | 7.2 | 410 | 25.4 | No cracking and stickiness |
| Example 4 | 0.34 | 1.3 | 7.4 | 405 | 25.3 | No cracking and stickiness |
| Example 5 | 0.36 | 1.2 | 7.1 | 415 | 25.6 | No cracking and stickiness |
| Example 6 | 0.41 | 1.3 | 7.1 | 402 | 25.6 | No cracking and stickiness |
| Example 7 | 0.32 | 1.2 | 7.7 | 465 | 25.3 | No cracking and stickiness |
| Example 8 | 0.31 | 1.2 | 7.1 | 465 | 25.4 | No cracking and stickiness |
| Example 9 | 0.33 | 1.1 | 8.5 | 470 | 25.1 | No cracking and stickiness |
| Example 10 | 4.2 | 1.2 | 8.0 | 401 | 26.1 | No cracking and stickiness |
| Test example 1 | 4.3 | 1.4 | 8.2 | 360 | 26.2 | No cracking and stickiness |
| Test example 2 | 0.41 | 5.9 | 8.3 | 340 | 30 | No cracking and stickiness |
| Test example 3 | 0.38 | 4.3 | 5.3 | 550 | 29 | Cracking and stickiness |
| Comparative example 1 | 0.32 | 1.2 | 6.3 | 385 | 25.6 | No cracking and stickiness |
| Comparative example 2 | 0.31 | 3.4 | 7.4 | 434 | 25.3 | No cracking and stickiness |
| Comparative example 3 | 0.31 | 5.8 | 7.2 | 430 | 29.5 | No cracking and stickiness |
As can be seen from Table 1, the gel fraction of the temporary protective coating for aqueous interpenetrating network structure urethane-modified acrylate equipment obtained in examples 1 to 10 can be less than 0.5%, the tensile strength can be more than 7MPa, the elongation at break can be more than 400%, and the surface tension can be less than 26 mN/m.
Examples 1-10, preparation of coatings from difunctional polyester diols prepared with 1, 8-octanediol and 1, 2-octanediol, the long chain side groups in 1, 2-octanediol had lower polarity, and the force acting between the long chain side groups and the substrate molecules was small, resulting in low peel strength. The comparative example 1 has a more obvious reduction in tensile strength and elongation at break than the example 1, while the peel strength and surface tension are the same, and the comparative example 2 has a smaller difference in tensile strength and elongation at break and a larger difference in peel strength and surface tension than the example 1, which shows that the addition of a certain amount of 1, 2-octanediol to prepare a resin can reduce the surface tension and peel strength and also can reduce the tensile strength and elongation at break, and the resin prepared from 1, 8-octanediol can improve the elongation at break and tensile strength, but has a higher surface tension and peel strength. In examples 1-6, 1, 2-octanediol and 1, 8-octanediol were used in combination, 1, 2-octanediol could have a certain internal plasticization effect, 1, 8-octanediol had good flexibility for improving mechanical properties, and urethane hard segment aggregation in polyurethane was reduced, so that when used in combination, surface tension and peel strength could be reduced, and elongation at break and tensile strength could be improved.
In examples 7 to 10, when polycaprolactone 1000, polypropylene oxide ether glycol, and home-made polyester glycol were used in combination, they also exhibited tensile strength and elongation at break, and also exhibited excellent aging resistance. The performance is more excellent when the modified hexamethylene diamine is used in combination with hexamethylene diamine, and the gel rate is lower.
Compared with example 6, the gel rate of example 1 is much higher than that of example 6, because hexamethylenediamine is used as primary aliphatic amine, the reaction speed with isocyanate is too fast, and the hexamethylenediamine has strong hydrophilicity and is easy to chain-extend and crosslink with isocyanate in water phase to form gel. The modified hexamethylene diamine has poor hydrophilicity, certain steric hindrance secondary amine and low reactivity with isocyanic acid radical. The modified hexamethylene diamine can enter latex particles to react with isocyanic acid radical for crosslinking and curing, and the gel rate is low.
The peel strength of test example 2 is much higher than that of example 6. Because the self-made polyester diol molecular chain contains the side group with lower polarity, the interaction between the temporary protective coating and the substrate can be reduced, and the peeling strength between the peelable coating and the substrate is reduced.
The strippable paint of test example 3 had poor resistance to artificially accelerated aging compared to example 6. Because the methylene connected with oxygen atoms in the polypropylene oxide ether dihydric alcohol DL-1000D is more active, degradation and crosslinking reaction occur through photo-oxidative aging, and the methylene of the self-made polyester dihydric alcohol is more stable. Therefore, the aging resistance of the temporary protective coating for the waterborne interpenetrating network structure polyurethane modified acrylate equipment in the embodiment 6 is excellent.
The data analysis shows that the waterborne interpenetrating network structure polyurethane modified acrylate equipment temporary protective coating prepared by using the self-made polyester diol and polycaprolactone 1000 or polypropylene oxide ether diol DL-1000D and the modified hexamethylenediamine in combination has the advantages of low peel strength, excellent weather resistance, low surface tension and certain self-cleaning effect.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. An interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating is characterized by comprising the following raw materials in parts by weight: 75-85 parts of polyurethane modified acrylate emulsion, 0.3-0.8 part of defoaming agent, 0.4-1 part of flatting agent, 1-4 parts of thixotropic agent, 0.5-2.5 parts of wetting dispersant, 5-10 parts of strippable auxiliary agent and 1-10 parts of deionized water;
the polyurethane modified acrylate emulsion comprises the following raw materials: 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 0-2 parts of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water;
the hydrophilic organic silicon modified polyurethane prepolymer comprises the following raw materials in parts by weight: 30-40 parts of polyester diol, 0-10 parts of polycaprolactone diol, 0-10 parts of polypropylene oxide ether diol, 15-20 parts of hexamethylene diisocyanate, 15-20 parts of isophorone diisocyanate, 6-10 parts of a hydrophilic chain extender, 1-3 parts of trimethylolpropane, 5-12 parts of hydroxypropyl silicone oil and 0.1-0.3 part of phenylmercuric acetate;
the polyester diol is prepared from the following raw materials, by weight, 14.8 parts of adipic acid, 22 parts of hexanediol, 16 parts of terephthalic acid, 10-15 parts of 1, 8-octanediol, 15-20 parts of 1, 2-octanediol and 14.2 parts of phthalic anhydride;
the preparation method of the modified hexamethylene diamine comprises the following steps:
preparing 35-40 parts of butyl acrylate, 25-28 parts of methyl acrylate and 30-40 parts of hexamethylene diamine according to parts by weight;
adding hexamethylene diamine into a reaction kettle, then dropwise adding butyl acrylate into the reaction kettle, keeping the temperature below 35 ℃, and reacting for 2 hours; then adding methyl acrylate dropwise, keeping the temperature below 35 ℃ and reacting for 2 hours; then the reaction is continued for 3h at 90 ℃, and the heating is stopped, thus obtaining the modified hexamethylene diamine.
2. The interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, wherein the polyurethane modified acrylate emulsion comprises the following raw materials in parts by weight: 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 1 part of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water.
3. The interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, wherein the preparation method of the hydrophilic silicone modified polyurethane prepolymer comprises the steps of sequentially adding a hydrophilic chain extender, trimethylolpropane, hexamethylene diisocyanate, isophorone diisocyanate, phenylmercuric acetate, polyester diol, polycaprolactone diol, polypropylene oxide ether diol and hydroxypropyl silicone oil into a reaction kettle, reacting for 3 hours at 80-85 ℃, stopping heating after the content of isocyanate reaches a theoretical value, and obtaining the hydrophilic silicone modified polyurethane prepolymer.
4. The interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, wherein the preparation method of the polyester diol comprises the following steps:
adding adipic acid, hexanediol, terephthalic acid, 1, 8-octanediol, 1, 2-octanediol and phthalic anhydride into a four-mouth bottle with vacuumizing, a bayonet condenser and nitrogen protection, gradually heating to 90-110 ℃, reacting for 20min, gradually heating to 150-160 ℃, reacting for 1h, continuously heating to 220-230 ℃, controlling the temperature of column heads to be lower than 98 ℃, reacting for 5-6h, and stopping heating after the acid value is determined to be below 3mgKOH/g to obtain the polyester dihydric alcohol.
5. The interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, wherein the preparation method of the hydrophilic chain extender comprises the following steps:
adding phthalic anhydride into triethanolamine at 45 ℃ in 4 batches averagely, controlling the temperature not to exceed 50 ℃, continuing to react for 2 hours at 60 ℃, and stopping heating to obtain the hydrophilic chain extender.
6. The interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, wherein the preparation method of the polyurethane modified acrylate emulsion comprises the following steps:
preparing 20-40 parts of hydrophilic organic silicon modified polyurethane prepolymer, 4-8 parts of modified hexamethylene diamine, 0-2 parts of hexamethylene diamine, 2-10 parts of butyl methacrylate, 3-8 parts of isooctyl acrylate, 1-3 parts of emulsifier SR-10, 1-3 parts of emulsifier ER-10, 1-3 parts of hexanediol diacrylate, 0.2-0.8 part of ammonium persulfate, 0.3-0.6 part of sodium bicarbonate and 40-50 parts of deionized water for later use;
mixing the hydrophilic organic silicon modified polyurethane prepolymer, butyl methacrylate, isooctyl acrylate, an emulsifier SR-10, an emulsifier ER-10 and hexanediol diacrylate, and stirring at the stirring speed of 100-;
setting the rotating speed at 800-;
D. adding the pre-emulsion into a reaction kettle with nitrogen protection, mechanical stirring and a spherical condenser tube, gradually heating to 80 ℃ at 70 ℃ according to the speed of 5-10 ℃/min, reacting for 3 hours, continuing to react for 2 hours at 90 ℃, and stopping heating to obtain the waterborne interpenetrating network structure polyurethane modified acrylate emulsion.
7. The preparation method of the interpenetrating network structure polyurethane modified acrylate self-cleaning peelable coating according to claim 1, comprising the following steps: stirring the polyurethane modified acrylate emulsion, the defoaming agent and the leveling agent for 10-15min at a stirring speed of 500-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394285.6A CN114716898B (en) | 2022-04-15 | 2022-04-15 | Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394285.6A CN114716898B (en) | 2022-04-15 | 2022-04-15 | Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114716898A CN114716898A (en) | 2022-07-08 |
| CN114716898B true CN114716898B (en) | 2022-09-23 |
Family
ID=82244731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210394285.6A Active CN114716898B (en) | 2022-04-15 | 2022-04-15 | Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114716898B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010139222A1 (en) * | 2009-06-01 | 2010-12-09 | Zhong Wenjun | Polyurethane-modified acrylic resin and preparing method thereof |
| CN106967357A (en) * | 2016-01-13 | 2017-07-21 | 海洋化工研究院有限公司 | Environment-friendly type aqueous Stripable paint and preparation |
| CN107286303A (en) * | 2017-07-01 | 2017-10-24 | 中山大学 | A kind of aqueous polyurethane acrylate emulsion and its aqueous ink used for plastic of preparation |
| CN108276892A (en) * | 2018-03-02 | 2018-07-13 | 山东七维新材料有限公司 | A kind of aqueous Stripable paint and preparation method thereof |
| WO2018182104A1 (en) * | 2017-03-29 | 2018-10-04 | 주식회사 빅스 | Hydrophilic water-dispersed polyurethane resin for textile skin coating and method for producing hydrophilic film using same |
| CN110713705A (en) * | 2019-10-17 | 2020-01-21 | 广东工业大学 | Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof |
| CN111635501A (en) * | 2020-06-29 | 2020-09-08 | 佛山市三水联美化工有限公司 | PU resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0532753A (en) * | 1991-07-26 | 1993-02-09 | Dainippon Ink & Chem Inc | Novel polyester polyol and polyurethane resin composition using the same |
-
2022
- 2022-04-15 CN CN202210394285.6A patent/CN114716898B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010139222A1 (en) * | 2009-06-01 | 2010-12-09 | Zhong Wenjun | Polyurethane-modified acrylic resin and preparing method thereof |
| CN106967357A (en) * | 2016-01-13 | 2017-07-21 | 海洋化工研究院有限公司 | Environment-friendly type aqueous Stripable paint and preparation |
| WO2018182104A1 (en) * | 2017-03-29 | 2018-10-04 | 주식회사 빅스 | Hydrophilic water-dispersed polyurethane resin for textile skin coating and method for producing hydrophilic film using same |
| CN107286303A (en) * | 2017-07-01 | 2017-10-24 | 中山大学 | A kind of aqueous polyurethane acrylate emulsion and its aqueous ink used for plastic of preparation |
| CN108276892A (en) * | 2018-03-02 | 2018-07-13 | 山东七维新材料有限公司 | A kind of aqueous Stripable paint and preparation method thereof |
| CN110713705A (en) * | 2019-10-17 | 2020-01-21 | 广东工业大学 | Water-based polyurethane emulsion with interpenetrating network structure and preparation method and application thereof |
| CN111635501A (en) * | 2020-06-29 | 2020-09-08 | 佛山市三水联美化工有限公司 | PU resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114716898A (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109761834B (en) | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating | |
| KR100483170B1 (en) | Aqueous coating composition for the manufacture of precoated metal | |
| CN104559617B (en) | A kind of application type aqueous dual-component fluorocarbon coating and its preparation and application | |
| CN111019504B (en) | Waterborne polyurethane coating composition and application thereof | |
| JP5388405B2 (en) | Polyisocyanate composition and two-component polyurethane composition | |
| JP2013506745A (en) | Polyurethane formulation with high green strength and gun ability | |
| CN108929423B (en) | Nonionic emulsifier for water-based epoxy resin and preparation method and application thereof | |
| CN112300682A (en) | Thin-coating type solvent-free coating for mechanical engineering equipment and preparation method thereof | |
| CN114806381B (en) | Anti-graffiti anti-sticking coating and preparation method thereof | |
| CN108239457B (en) | Water-based peelable glue, and preparation method and application thereof | |
| CN114716898B (en) | Interpenetrating network structure polyurethane modified acrylate self-cleaning strippable coating | |
| CN113025132A (en) | Water-based organic silicon modified fluorocarbon wind power blade coating and preparation method thereof | |
| CN112625581A (en) | Self-repairing real stone paint coating and preparation method thereof | |
| CN110845938B (en) | Toughening modified water-based epoxy resin waterproof coating and preparation method thereof | |
| CA2209753C (en) | New polyamines and their use in aqueous coating compositions | |
| CN114920896B (en) | Water-based polycarbodiimide and preparation method and application thereof | |
| JP2009149801A (en) | Polyisocyanate composition and two-liquid type polyurethane composition | |
| CN115558404A (en) | Preparation method of water-based high-gloss polyurethane finish paint suitable for engineering machinery | |
| CN111019496B (en) | Water-dispersible two-component polyurea coating composition with excellent weather resistance and elasticity, preparation method and application thereof | |
| CN101157843A (en) | Preparation method of environment-friendly type aqueous polyurethane hot sol for poncho artificial leather | |
| CN113773744A (en) | Water-based alkyd anticorrosive paint and preparation method thereof | |
| CN112608626A (en) | Waterborne polyurethane-polyacrylic acid-based self-repairing real stone paint and preparation method thereof | |
| CN114958133B (en) | Bio-based modified low-temperature-resistant quick-setting asphalt emulsion coating and preparation method thereof | |
| CN115260228B (en) | Silicon-containing compound and preparation method thereof, and single-component polyurethane waterproof coating and preparation method thereof | |
| CN117701054B (en) | Blending water for water paint and preparation method thereof |
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 |