A coating thickener based on pentaerythritol triallyl ether and a coating
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHENZHEN PRECHEM FINE CHEM CO LTD
- Filing Date
- 2026-03-09
- Publication Date
- 2026-06-09
Smart Images
Figure CN122167671A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of coating processing technology, and relates to a coating thickener and coating based on pentaerythritol triallyl ether. Background Technology
[0002] Pentaerythritol triallyl ether is an important multifunctional compound. Existing technology (CN117069568B) discloses a method for preparing highly selective pentaerythritol triallyl ether, which achieves a selectivity of over 80% through multi-stage water separation control. However, currently, when preparing the above-mentioned pentaerythritol triallyl ether into downstream products such as crosslinking agents and thickeners, a complex purification process is still required, otherwise the performance of the coating will be affected. Summary of the Invention
[0003] The purpose of this invention is to provide a coating thickener and coating based on pentaerythritol triallyl ether, thereby solving the above-mentioned problems.
[0004] The technical solution adopted in this invention is as follows: A coating thickener based on pentaerythritol triallyl ether, wherein the coating thickener is prepared by in-situ copolymerization modification of a four-stage dehydration reaction system of pentaerythritol triallyl ether; the raw materials for preparing the coating thickener include raw materials for preparing pentaerythritol triallyl ether and modified raw materials; The raw materials for preparing pentaerythritol triallyl ether include the following components: 250 parts by weight of pentaerythritol, 4280-4285 parts by weight of 50% sodium hydroxide solution, 100-105 parts by weight of tetrabutylammonium bromide, 20-25 parts by weight of dimethyl sulfoxide, and 4860-4863 parts by weight of allyl chloride. The modified raw material comprises the following components: 74-76 parts by weight of polyethylene glycol methyl methacrylate, 54-56 parts by weight of acrylic acid, 14-16 parts by weight of dodecyl acrylate, 2-3 parts by weight of ethylene glycol dimethacrylate, 3-4 parts by weight of ammonium persulfate, 1.7-1.9 parts by weight of dodecyl mercaptan, glacial acetic acid, 4.4-4.6 parts by weight of nonylphenol polyoxyethylene ether, 1.1-1.3 parts by weight of triethyl phosphate, 320 parts by weight of deionized water, 17-19 parts by weight of triethanolamine, and 0.3 parts by weight of sodium bisulfite.
[0005] Furthermore, the pentaerythritol triallyl ether four-stage water separation reaction system was prepared by the following method: First stage: 250 parts by weight of pentaerythritol are added to the reactor, followed by 525 parts by weight of 50% sodium hydroxide solution, 11 parts by weight of tetrabutylammonium bromide catalyst, and 23 parts by weight of dimethyl sulfoxide. The temperature is raised to 100°C and maintained for 30 minutes. The temperature of the reaction system is controlled at 95-100°C. Without water separation, 465 parts by weight of allyl chloride are added dropwise within 5 hours. Second stage: 2403 parts by weight of 50% caustic soda solution and 50 parts by weight of tetrabutylammonium bromide catalyst were added to the reaction vessel. The temperature of the reaction system was controlled at 95-100℃. After adding 857 parts by weight of allyl chloride, water separation began until another 1271 parts by weight of allyl chloride was added. The total time for adding the above allyl chloride was 10 hours. Third stage: 1169 parts by weight of 50% caustic soda solution and 37 parts by weight of tetrabutylammonium bromide catalyst are added to the reaction vessel. The temperature of the reaction system is controlled at 90-100℃. Under the condition of continuous water separation, 1950 parts by weight of allyl chloride are added dropwise within 11 hours. Fourth stage: 187 parts by weight of 50% sodium hydroxide solution and 5 parts by weight of tetrabutylammonium bromide catalyst were added to the reactor. The temperature of the reaction system was controlled at 90-100℃. Under continuous water separation, 318 parts by weight of allyl chloride were added dropwise within 2 hours. The molar fraction of pentaerythritol triallyl ether in the reaction product was detected to be 82%. The temperature was maintained at 85-90℃ to obtain the four-stage water separation reaction system of pentaerythritol triallyl ether.
[0006] Furthermore, the method for preparing a coating thickener by in-situ copolymerization modification of a pentaerythritol triallyl ether four-stage dehydration reaction system includes the following steps: S1.1 After the fourth stage reaction, turn on the vacuum system of the reactor and control the vacuum degree to -0.08~-0.09MPa and the temperature to 85~90℃, and remove light weights under reduced pressure for 30 minutes; then slowly add glacial acetic acid dropwise to the pentaerythritol triallyl ether four-stage water separation reaction system while stirring (300r / min) to adjust the pH of the pentaerythritol triallyl ether four-stage water separation reaction system to 7~8; then introduce high-purity nitrogen into the reactor for gas phase replacement for 20 minutes; then insert the nitrogen delivery tube into the bottom of the liquid phase and bubble the liquid phase to remove oxygen for 30 minutes, controlling the bubbling rate to 5~8L / min, while adding 0.3 parts by weight of sodium bisulfite; then maintain a slightly positive pressure nitrogen atmosphere (0.01~0.02MPa) in the reactor until the reaction is completed; S1.2. Mix 75 parts by weight of polyethylene glycol methyl methacrylate, 55 parts by weight of acrylic acid, 15 parts by weight of dodecyl acrylate, and 2.5 parts by weight of ethylene glycol dimethacrylate, and stir evenly to obtain a modified monomer mixture. S1.3. Dissolve 4 parts by weight of ammonium persulfate in 60 parts by weight of deionized water to prepare an initiator solution; S1.4 At 90-95℃, add 4.5 parts by weight of nonylphenol polyoxyethylene ether, 1.2 parts by weight of triethyl phosphate, and 80% dodecyl mercaptan to the pentaerythritol triallyl ether four-stage water separation reaction system treated in step S1. Stir to form a stable aqueous emulsion system. At the same time, add the modified monomer mixture and initiator solution dropwise over 5 hours. After 2 hours of dropwise addition, add the remaining dodecyl mercaptan. After the dropwise addition is completed, add 0.5 parts by weight of ammonium persulfate aqueous solution (concentration of 10% by mass) to the reaction system and keep it at 90℃ for 3 hours. Reduce the temperature of the reaction system to 50℃, add 18 parts by weight of triethanolamine, and then slowly add 260 parts by weight of deionized water. After stirring for 1 hour, filter to obtain the liquid coating thickener.
[0007] Furthermore, the average molecular weight of the polyethylene glycol methyl methacrylate is 950-1000.
[0008] Furthermore, the coating based on pentaerythritol triallyl ether as a coating thickener includes component A and component B; Component A comprises the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 75-80 parts pigments and fillers, 0.5-1 parts dispersant, 0.2-0.3 parts defoamer, 3-5 parts film-forming agent, 1.4-1.5 parts pentaerythritol triallyl ether-based paint thickener, 30 parts deionized water, and pH adjuster; Component B is a curing agent adapted to isocyanate epoxy emulsion.
[0009] Furthermore, the amount of component B added is 40% of the mass of the isocyanate-modified epoxy emulsion.
[0010] Further, calculated separately, component B comprises the following components by weight fraction: 80-85 parts of an amine adduct type aqueous epoxy curing agent with an amine value of 200 mg KOH / g, 5-8 parts of ethylene glycol butyl ether acetate, 2-3 parts of γ-aminopropyltriethoxysilane coupling agent, and 5-7 parts of deionized water.
[0011] Further, the pigments and fillers comprise the following components in parts by weight: 25 parts titanium dioxide, 15 parts zinc phosphate, 10 parts aluminum tripolyphosphate, 10 parts talc, and 5 parts precipitated barium sulfate; the dispersant is a polycarboxylate-type polymeric dispersant; the defoamer is an organosilicon polyether composite high-temperature defoamer; the film-forming agent comprises dodecyl alcohol ester and propylene glycol butyl ether in a mass ratio of 3:1; and the pH adjuster is AMP-95 pH adjuster.
[0012] Further, the isocyanate-modified epoxy emulsion was prepared by the following method, by weight: 40 parts of epoxy resin E-44, 15 parts of isophorone diisocyanate, and 0.05 parts of dibutyltin dilaurate were added to a reactor, and the mixture was heated to 80°C under nitrogen protection and reacted at a constant temperature for 2 hours; then 8 parts of polyethylene glycol monomethyl ether MPEG-400 and 3 parts of dimethylolpropionic acid were added to the reactor, and the reaction was continued at 80°C for 3 hours. The reaction system was then cooled to 45°C, and 2.5 parts of triethylamine were added. After stirring for 15 minutes, 120 parts of deionized water were slowly added dropwise to the reactor under high-speed shear (1500 r / min) conditions, and emulsification was carried out for 30 minutes. Then the temperature was raised to 50°C, and 0.8 parts of ethylenediamine were added to react for 1 hour. After the reaction was completed, the temperature was lowered to below 30°C, and the mixture was filtered to obtain the isocyanate epoxy emulsion.
[0013] Furthermore, the coating is prepared by the following method: S1. Preparation of Component A: After mixing deionized water, dispersant, and defoamer evenly, slowly add pigments and fillers under stirring. After the addition is complete, adjust the stirring speed to 1200 r / min and disperse at high speed for 20 minutes. Then reduce the stirring speed to 600 r / min and maintain the stirring speed. Add isocyanate-modified epoxy emulsion, film-forming agent, and pentaerythritol triallyl ether-based coating thickener in sequence. After the addition is complete, continue stirring for 10-12 minutes. Then add AMP-95 pH adjuster dropwise while stirring to adjust the pH value of the Component A system to 7-8. Continue stirring for 5 minutes to obtain Component A. S2. Preparation of Component B: Add amine adduct type waterborne epoxy curing agent, ethylene glycol butyl ether acetate, γ-aminopropyltriethoxysilane coupling agent, and deionized water to a mixing container in sequence. Stir at 800 r / min for 8-10 minutes at room temperature to obtain component B. After the preparation of components A and B is completed, store them separately. Mix them in proportion before use and stir evenly to obtain the coating for application.
[0014] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. The present invention discloses a coating thickener based on pentaerythritol triallyl ether, which is modified by in-situ copolymerization. The copolymerization modification is carried out in-situ in a four-stage water separation reaction system of pentaerythritol triallyl ether. Without the need for purification of pentaerythritol triallyl ether, a thickener that can be used in isocyanate modified epoxy emulsion coatings and will not adversely affect the performance of the coating is obtained. 2. The thickener of this invention introduces both hydrophobic long chains and hydrophilic segments to form an associated structure. This structure provides high apparent viscosity under low shear through intermolecular hydrophobic association, preventing pigment and filler sedimentation. Under high shear (such as spraying or brushing), the associated structure is reversibly destroyed, the viscosity decreases, and the coating is given excellent leveling properties. At the same time, the viscosity recovers rapidly after shear removal, effectively preventing sagging. Attached Figure Description
[0015] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort, wherein: Figure 1 This is the preparation method of the coating in this application. Detailed Implementation
[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.
[0017] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.
[0018] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.
[0019] The features and performance of the present invention will be further described in detail below with reference to embodiments.
[0020] A coating thickener based on pentaerythritol triallyl ether is prepared by in-situ copolymerization modification of a four-stage dehydration reaction system of pentaerythritol triallyl ether; the raw materials for preparing the coating thickener include raw materials for preparing pentaerythritol triallyl ether and modified raw materials; In the following examples, the raw materials for preparing pentaerythritol triallyl ether include the following components: 250 parts by weight of pentaerythritol, 4280-4285 parts by weight of 50% sodium hydroxide solution, 100-105 parts by weight of tetrabutylammonium bromide, 20-25 parts by weight of dimethyl sulfoxide, and 4860-4863 parts by weight of allyl chloride. In the following examples, the modified raw material includes the following components: 74-76 parts by weight of polyethylene glycol methyl methacrylate, 54-56 parts by weight of acrylic acid, 14-16 parts by weight of dodecyl acrylate, 2-3 parts by weight of ethylene glycol dimethacrylate, 3-4 parts by weight of ammonium persulfate, 1.7-1.9 parts by weight of dodecyl mercaptan, glacial acetic acid, 4.4-4.6 parts by weight of nonylphenol polyoxyethylene ether, 1.1-1.3 parts by weight of triethyl phosphate, 320 parts by weight of deionized water, 17-19 parts by weight of triethanolamine, and 0.3 parts by weight of sodium bisulfite.
[0021] In the following examples, the average molecular weight of the polyethylene glycol methyl methacrylate is 950-1000.
[0022] In the following examples, a coating based on pentaerythritol triallyl ether thickener includes component A and component B; Component A comprises the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 75-80 parts pigments and fillers, 0.5-1 parts dispersant, 0.2-0.3 parts defoamer, 3-5 parts film-forming agent, 1.4-1.5 parts pentaerythritol triallyl ether-based paint thickener, 30 parts deionized water, and pH adjuster; Component B is a curing agent adapted to isocyanate epoxy emulsion.
[0023] In the following examples, calculated independently, component B comprises the following components by weight fraction: 80-85 parts of an amine adduct type aqueous epoxy curing agent with an amine value of 200 mg KOH / g, 5-8 parts of ethylene glycol butyl ether acetate, 2-3 parts of γ-aminopropyltriethoxysilane coupling agent, and 5-7 parts of deionized water.
[0024] In the following examples, the isocyanate-modified epoxy emulsion was prepared by the following method, by weight: 40 parts of epoxy resin E-44, 15 parts of isophorone diisocyanate, and 0.05 parts of dibutyltin dilaurate were added to a reactor, and the mixture was heated to 80°C under nitrogen protection and reacted at a constant temperature for 2 hours; then 8 parts of polyethylene glycol monomethyl ether MPEG-400 and 3 parts of dimethylolpropionic acid were added to the reactor, and the reaction was continued at 80°C for 3 hours. The reaction system was then cooled to 45°C, and 2.5 parts of triethylamine were added. After stirring for 15 minutes, 120 parts of deionized water were slowly added dropwise to the reactor under high-speed shear (1500 r / min) conditions, and emulsification was carried out for 30 minutes. Subsequently, the temperature was raised to 50°C, and 0.8 parts of ethylenediamine were added to react for 1 hour. After the reaction was completed, the temperature was lowered to below 30°C, and the mixture was filtered to obtain the isocyanate epoxy emulsion.
[0025] Example 1 The present invention provides a coating thickener based on pentaerythritol triallyl ether, which is prepared by the following method: Step 1: First stage: 250 parts by weight of pentaerythritol are added to the reactor, followed by 525 parts by weight of 50% sodium hydroxide solution, 11 parts by weight of tetrabutylammonium bromide catalyst, and 23 parts by weight of dimethyl sulfoxide. The temperature is raised to 100°C and maintained for 30 minutes. The temperature of the reaction system is controlled at 95-100°C. Without water separation, 465 parts by weight of allyl chloride are added dropwise within 5 hours. Second stage: 2403 parts by weight of 50% caustic soda solution and 50 parts by weight of tetrabutylammonium bromide catalyst were added to the reaction vessel. The temperature of the reaction system was controlled at 95-100℃. After adding 857 parts by weight of allyl chloride, water separation began until another 1271 parts by weight of allyl chloride was added. The total time for adding the above allyl chloride was 10 hours. Third stage: 1169 parts by weight of 50% caustic soda solution and 37 parts by weight of tetrabutylammonium bromide catalyst are added to the reaction vessel. The temperature of the reaction system is controlled at 90-100℃. Under the condition of continuous water separation, 1950 parts by weight of allyl chloride are added dropwise within 11 hours. Fourth stage: 187 parts by weight of 50% sodium hydroxide solution and 5 parts by weight of tetrabutylammonium bromide catalyst were added to the reactor. The temperature of the reaction system was controlled at 90-100℃. Under continuous water separation, 318 parts by weight of allyl chloride were added dropwise within 2 hours. The molar fraction of pentaerythritol triallyl ether in the reaction product was detected to be 82%. The temperature was maintained at 85-90℃ to obtain the four-stage water separation reaction system of pentaerythritol triallyl ether. Step Two: S1.1 After the fourth stage reaction, turn on the vacuum system of the reactor and control the vacuum degree to -0.08~-0.09MPa and the temperature to 85~90℃, and remove light weights under reduced pressure for 30 minutes; then slowly add glacial acetic acid dropwise to the pentaerythritol triallyl ether four-stage water separation reaction system while stirring (300r / min) to adjust the pH of the pentaerythritol triallyl ether four-stage water separation reaction system to 7~8; then introduce high-purity nitrogen into the reactor for gas phase replacement for 20 minutes; then insert the nitrogen delivery tube into the bottom of the liquid phase and bubble the liquid phase to remove oxygen for 30 minutes, controlling the bubbling rate to 5~8L / min, while adding 0.3 parts by weight of sodium bisulfite; then maintain a slightly positive pressure nitrogen atmosphere (0.01~0.02MPa) in the reactor until the reaction is completed; S1.2. Mix 75 parts by weight of polyethylene glycol methyl methacrylate, 55 parts by weight of acrylic acid, 15 parts by weight of dodecyl acrylate, and 2.5 parts by weight of ethylene glycol dimethacrylate, and stir evenly to obtain a modified monomer mixture. S1.3. Dissolve 4 parts by weight of ammonium persulfate in 60 parts by weight of deionized water to prepare an initiator solution; S1.4 At 95℃, add 4.5 parts by weight of nonylphenol polyoxyethylene ether, 1.2 parts by weight of triethyl phosphate, and 80% dodecyl mercaptan to the pentaerythritol triallyl ether four-stage water separation reaction system treated in step S1. Stir to form a stable aqueous emulsion system. At the same time, add the modified monomer mixture and initiator solution dropwise over 5 hours. After 2 hours of dropwise addition, add the remaining dodecyl mercaptan. After the dropwise addition is completed, add 0.5 parts by weight of ammonium persulfate aqueous solution (concentration of 10% by mass) to the reaction system and keep it at 90℃ for 3 hours. Reduce the temperature of the reaction system to 50℃, add 18 parts by weight of triethanolamine, and then slowly add 260 parts by weight of deionized water. After stirring for 1 hour, filter to obtain the liquid coating thickener.
[0026] Example 2 This embodiment provides a coating thickener. Based on Embodiment 1, the difference between this embodiment and Embodiment 1 is that the component ratio in step two of the coating thickener preparation method is different, while step one remains the same. Step two consists of the following steps: Step Two: S1.1 After the fourth stage reaction, turn on the vacuum system of the reactor and control the vacuum degree to -0.08~-0.09MPa and the temperature to 85~90℃, and remove light weights under reduced pressure for 30 minutes; then slowly add glacial acetic acid dropwise to the pentaerythritol triallyl ether four-stage water separation reaction system while stirring (300r / min) to adjust the pH of the pentaerythritol triallyl ether four-stage water separation reaction system to 7~8; then introduce high-purity nitrogen into the reactor for gas phase replacement for 20 minutes; then insert the nitrogen delivery tube into the bottom of the liquid phase and bubble the liquid phase to remove oxygen for 30 minutes, controlling the bubbling rate to 5~8L / min, while adding 0.3 parts by weight of sodium bisulfite; then maintain a slightly positive pressure nitrogen atmosphere (0.01~0.02MPa) in the reactor until the reaction is completed; S1.2. Mix 74 parts by weight of polyethylene glycol methyl methacrylate, 54 parts by weight of acrylic acid, 14 parts by weight of dodecyl acrylate and 2 parts by weight of ethylene glycol dimethacrylate, and stir evenly to obtain a modified monomer mixture. S1.3. Dissolve 4 parts by weight of ammonium persulfate in 60 parts by weight of deionized water to prepare an initiator solution; S1.4 At 95℃, add 4.4 parts by weight of nonylphenol polyoxyethylene ether, 1.1 parts by weight of triethyl phosphate, and 80% dodecyl mercaptan to the pentaerythritol triallyl ether four-stage water separation reaction system treated in step S1. Stir to form a stable aqueous emulsion system. At the same time, add the modified monomer mixture and initiator solution dropwise over 5 hours. After 2 hours of dropwise addition, add the remaining dodecyl mercaptan. After the dropwise addition is completed, add 0.5 parts by weight of ammonium persulfate aqueous solution (concentration of 10% by mass) to the reaction system and keep it at 90℃ for 3 hours. Reduce the temperature of the reaction system to 50℃, add 17 parts by weight of triethanolamine, and then slowly add 260 parts by weight of deionized water. After stirring for 1 hour, filter to obtain the liquid coating thickener.
[0027] Example 3 This embodiment provides a coating thickener. Unlike Example 1, the component ratio in step two of the coating thickener preparation method is different, while step one remains the same. Step two consists of the following steps: Step Two: S1.1 After the fourth stage reaction, turn on the vacuum system of the reactor and control the vacuum degree to -0.08~-0.09MPa and the temperature to 85~90℃, and remove light weights under reduced pressure for 30 minutes; then slowly add glacial acetic acid dropwise to the pentaerythritol triallyl ether four-stage water separation reaction system while stirring (300r / min) to adjust the pH of the pentaerythritol triallyl ether four-stage water separation reaction system to 7~8; then introduce high-purity nitrogen into the reactor for gas phase replacement for 20 minutes; then insert the nitrogen delivery tube into the bottom of the liquid phase and bubble the liquid phase to remove oxygen for 30 minutes, controlling the bubbling rate to 5~8L / min, while adding 0.3 parts by weight of sodium bisulfite; then maintain a slightly positive pressure nitrogen atmosphere (0.01~0.02MPa) in the reactor until the reaction is completed; S1.2. Mix 76 parts by weight of polyethylene glycol methyl methacrylate, 56 parts by weight of acrylic acid, 16 parts by weight of dodecyl acrylate and 3 parts by weight of ethylene glycol dimethacrylate, and stir evenly to obtain a modified monomer mixture. S1.3. Dissolve 4 parts by weight of ammonium persulfate in 60 parts by weight of deionized water to prepare an initiator solution; S1.4 At 95℃, add 4.6 parts by weight of nonylphenol polyoxyethylene ether, 1.3 parts by weight of triethyl phosphate, and 80% dodecyl mercaptan to the pentaerythritol triallyl ether four-stage water separation reaction system treated in step S1. Stir to form a stable aqueous emulsion system. At the same time, add the modified monomer mixture and initiator solution dropwise over 5 hours. After 2 hours of dropwise addition, add the remaining dodecyl mercaptan. After the dropwise addition is completed, add 0.5 parts by weight of ammonium persulfate aqueous solution (concentration of 10% by mass) to the reaction system and keep it at 90℃ for 3 hours. Reduce the temperature of the reaction system to 50℃, add 19 parts by weight of triethanolamine, and then slowly add 260 parts by weight of deionized water. After stirring for 1 hour, filter to obtain the liquid coating thickener.
[0028] Example 4 This embodiment provides a coating based on the coating thickener prepared in Example 1, comprising component A and component B; Component A comprises the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 75 parts pigments and fillers, 0.5 parts dispersant, 0.2 parts defoamer, 3 parts film-forming agent, 1.4 parts pentaerythritol triallyl ether-based coating thickener, 30 parts deionized water, and pH adjuster. Component B is a curing agent adapted to isocyanate epoxy emulsion.
[0029] The amount of component B added is 40% of the mass of the isocyanate-modified epoxy emulsion.
[0030] Component B, when calculated separately, comprises the following components by weight fraction: 80 parts of an amine adduct type aqueous epoxy curing agent with an amine value of 200 mg KOH / g, 5 parts of ethylene glycol butyl ether acetate, 2 parts of γ-aminopropyltriethoxysilane coupling agent, and 5 parts of deionized water.
[0031] Independently calculated, the pigments and fillers comprise the following components in parts by weight: 25 parts titanium dioxide, 15 parts zinc phosphate, 10 parts aluminum tripolyphosphate, 10 parts talc, and 5 parts precipitated barium sulfate. The dispersant is a polycarboxylate-type polymeric dispersant; The defoamer is an organosilicon polyether composite high-temperature defoamer; The film-forming agent comprises dodecayl alcohol ester and propylene glycol butyl ether in a mass ratio of 3:1; The pH adjuster is AMP-95 pH adjuster.
[0032] like Figure 1 As shown, the coating is prepared by the following method: S1. Preparation of Component A: After mixing deionized water, dispersant, and defoamer evenly, slowly add pigments and fillers under stirring. After the addition is complete, adjust the stirring speed to 1200 r / min and disperse at high speed for 20 minutes. Then reduce the stirring speed to 600 r / min and maintain the stirring speed. Add isocyanate-modified epoxy emulsion, film-forming agent, and pentaerythritol triallyl ether-based coating thickener in sequence. After the addition is complete, continue stirring for 10-12 minutes. Then add AMP-95 pH adjuster dropwise while stirring to adjust the pH value of the Component A system to 7-8. Continue stirring for 5 minutes to obtain Component A. S2. Preparation of Component B: Add amine adduct type waterborne epoxy curing agent, ethylene glycol butyl ether acetate, γ-aminopropyltriethoxysilane coupling agent, and deionized water to a mixing container in sequence. Stir at 800 r / min for 8-10 minutes at room temperature to obtain component B. After the preparation of components A and B is completed, store them separately. Mix them in proportion before use and stir evenly to obtain the coating for application.
[0033] Example 5 Based on Example 4, this example provides a coating. Unlike Example 4, component A in this example includes the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 78 parts pigments and fillers, 0.8 parts dispersant, 0.3 parts defoamer, 4 parts film-forming agent, 1.5 parts pentaerythritol triallyl ether-based coating thickener (prepared in Example 1), 30 parts deionized water, and pH adjuster. Component B, when calculated separately, comprises the following components by weight fraction: 83 parts of an amine adduct type aqueous epoxy curing agent with an amine value of 200 mg KOH / g, 7 parts of ethylene glycol butyl ether acetate, 3 parts of γ-aminopropyltriethoxysilane coupling agent, and 6 parts of deionized water.
[0034] The remaining parts and preparation methods are the same as in Example 4.
[0035] Example 6 Based on Example 4, this embodiment provides a coating. Unlike Example 4, component A in this embodiment includes the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 80 parts pigments and fillers, 1 part dispersant, 0.3 parts defoamer, 5 parts film-forming agent, 1.5 parts pentaerythritol triallyl ether-based coating thickener (prepared in Example 1), 30 parts deionized water, and pH adjuster. Component B, when calculated separately, comprises the following components by weight fraction: 85 parts of an amine adduct type aqueous epoxy curing agent with an amine value of 200 mg KOH / g, 8 parts of ethylene glycol butyl ether acetate, 3 parts of γ-aminopropyltriethoxysilane coupling agent, and 7 parts of deionized water.
[0036] The remaining parts and preparation methods are the same as in Example 4.
[0037] Comparative Example 1 The coating thickener based on pentaerythritol triallyl ether provided in this comparative example is pentaerythritol triallyl ether with a purity of 99% (CAS No.: 1471-17-6).
[0038] Comparative Example 2 The pentaerythritol triallyl ether-based paint thickener provided in this comparative example is the product obtained only through step one of the reactions in Example 1: The pentaerythritol triallyl ether-based paint thickener provided in this comparative example is prepared by the following method: Step 1: First stage: 250 parts by weight of pentaerythritol are added to the reactor, followed by 525 parts by weight of 50% sodium hydroxide solution, 11 parts by weight of tetrabutylammonium bromide catalyst, and 23 parts by weight of dimethyl sulfoxide. The temperature is raised to 100°C and maintained for 30 minutes. The temperature of the reaction system is controlled at 95-100°C. Without water separation, 465 parts by weight of allyl chloride are added dropwise within 5 hours. Second stage: 2403 parts by weight of 50% caustic soda solution and 50 parts by weight of tetrabutylammonium bromide catalyst were added to the reaction vessel. The temperature of the reaction system was controlled at 95-100℃. After adding 857 parts by weight of allyl chloride, water separation began until another 1271 parts by weight of allyl chloride was added. The total time for adding the above allyl chloride was 10 hours. Third stage: 1169 parts by weight of 50% caustic soda solution and 37 parts by weight of tetrabutylammonium bromide catalyst are added to the reaction vessel. The temperature of the reaction system is controlled at 90-100℃. Under the condition of continuous water separation, 1950 parts by weight of allyl chloride are added dropwise within 11 hours. Fourth stage: 187 parts by weight of 50% sodium hydroxide solution and 5 parts by weight of tetrabutylammonium bromide catalyst were added to the reactor. The temperature of the reaction system was controlled at 90-100℃. Under continuous water separation, 318 parts by weight of allyl chloride were added dropwise within 2 hours. The molar fraction of pentaerythritol triallyl ether in the reaction product was detected to be 82%. The temperature was maintained at 85-90℃ to obtain the pentaerythritol triallyl ether four-stage water separation reaction system, which can be used directly as a thickener.
[0039] Comparative Example 3 Based on Example 1, unlike Example 1, this comparative example does not perform step S1.1 in the preparation of the coating thickener based on pentaerythritol triallyl ether, and does not treat the four-stage water separation reaction system of pentaerythritol triallyl ether obtained after the fourth stage of step one, while the rest are the same.
[0040] Comparative Example 4 Based on Example 1, the difference from Example 1 is that the modified raw material in this comparative example does not include polyethylene glycol methyl methacrylate, but all other aspects are the same.
[0041] Comparative Example 5 Based on Example 1, the difference from Example 1 is that the modified raw material in this comparative example does not include acrylic acid, but all other aspects are the same.
[0042] Comparative Example 6 Based on Example 1, the difference from Example 1 is that the modified raw materials in this comparative example do not include dodecyl acrylate, but all other aspects are the same.
[0043] Comparative Example 7 Based on Example 5, the difference from Example 5 is that epoxy resin E-44 is used instead of isocyanate modified epoxy emulsion in coating component A of this comparative example, while the proportions and preparation methods of the remaining components are the same.
[0044] Experimental Example 1 The thickening effect of the coating thickeners prepared in each embodiment and comparative example and their compatibility with other coating components were verified. The results are shown in Table 1. Test samples: Coating thickeners prepared in Examples 1, 2, and 3 Comparative samples: Comparative Example 1 (99% pure pentaerythritol triallyl ether), Comparative Example 2 (unmodified pentaerythritol triallyl ether reaction system), Comparative Example 3 (modified thickener without S1.1 treatment), Comparative Example 4 (thickener without polyethylene glycol methyl methacrylate), Comparative Example 5 (thickener without acrylic acid), Comparative Example 6 (thickener without dodecyl acrylate); Coating substrate (blank group, consisting of component A, without component B): the isocyanate-modified epoxy emulsion system prepared in Example 5 (component A, which contains all other components without the addition of thickener, is the blank coating system); Thickening effect testing method: Each sample (1.5 parts by weight, consistent with the thickener addition in Example 5) was added to the blank coating system. The mixture was stirred at 600 rpm for 10 minutes using a high-speed stirrer. The pH was adjusted to 7-8, and the mixture was allowed to stand for 30 minutes. The initial viscosity of the system at 25°C was measured using a rotational viscometer (NDJ-1 rotational viscometer). Simultaneously, the viscosity at different shear rates (30 rpm, 60 rpm, and 120 rpm) was also tested. Viscosity is measured in mPa. s (25℃, NDJ-1; rotational viscometer) Compatibility test of thickener with other components of coating: Add 6.5 parts by weight of each thickener of the experimental sample and control sample to the blank coating system, stir evenly, and let stand for 24h and 48h. Observe the appearance of the system (whether it is transparent and uniform, whether there are particles or flocculation), and at the same time test the pH stability of the system (pH change within 24h) to evaluate the compatibility of the thickener with isocyanate modified epoxy emulsion, pigments, fillers and additives in the coating; if layering, flocculation or pH change (change range > 0.5) occurs, it is judged as unqualified in terms of compatibility; Table 1 Performance testing of thickeners This application has a significant thickening effect and good compatibility with coating components.
[0045] Experimental Example 2 The coatings (construction coatings obtained by mixing component A and component B) prepared in Examples 4-6, Comparative Example 7, and Blank Control Coating (without any thickener, otherwise consistent with Example 5) were tested under the same test conditions (all test samples were tested under the same test conditions in the same performance test). The results are shown in Table 2.
[0046] Leveling test method: Select a flow coater with a fixed gap of 100μm, ensuring its surface is flat and smooth, without any wear or contaminant adhesion; prepare a clean, flat glass plate with a size of not less than 20cm×20cm; thoroughly stir the coating to be tested, place the flow coater at one end of the glass plate, and pour in an appropriate amount of epoxy coating to fill the gap of the flow coater; quickly and uniformly push the flow coater forward along the surface of the glass plate to evenly coat the coating on the glass plate to form a wet film; start timing from the moment the coating is completed, and under standard environmental conditions (temperature 23±2℃, relative humidity 50±5%), continuously observe the surface of the wet film using a 10x magnifying glass. When the surface of the wet film is completely smooth, without any visible brush marks, flow marks, or depressions, stop timing and record the time at this moment as the leveling time; Adhesion test method: Refer to standard GB / T 9286-2021 "Cross-cut test for paints and varnishes"; Neutral salt spray corrosion resistance: Refer to the standard neutral salt spray test (GB / T 10125-2021), test time 72h, observe whether there is rust, blistering, peeling or other conditions on the surface of the test piece (coated on Q235 steel structure test piece by spraying process (dry film thickness 50±5μm)); Water resistance: The coated test piece (coated on a Q235 steel structure test piece by spraying process (dry film thickness 50±5μm)) was immersed in deionized water at 25℃ for 14 days. After immersion, the surface condition was observed. Hardness: Refer to standard GB / T 6739-2022, pencil hardness.
[0047] Table 2 Basic Performance Tests of Coatings The pentaerythritol triallyl ether-based coating thickener prepared in this application can be used to prepare a water-resistant, corrosion-resistant, and workable isocyanate-modified epoxy emulsion coating that is fast-leveling, smooth, uniform, and flat, and can be used for basic protection of equipment, etc.
[0048] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A coating thickener based on pentaerythritol triallyl ether, characterized in that: The paint thickener is prepared by in-situ copolymerization modification of a pentaerythritol triallyl ether four-stage water separation reaction system; the raw materials for preparing the paint thickener include pentaerythritol triallyl ether preparation raw materials and modification raw materials; The raw materials for preparing pentaerythritol triallyl ether include the following components: 250 parts by weight of pentaerythritol, 4280-4285 parts by weight of 50% sodium hydroxide solution, 100-105 parts by weight of tetrabutylammonium bromide, 20-25 parts by weight of dimethyl sulfoxide, and 4860-4863 parts by weight of allyl chloride. The modified raw material comprises the following components: 74-76 parts by weight of polyethylene glycol methyl methacrylate, 54-56 parts by weight of acrylic acid, 14-16 parts by weight of dodecyl acrylate, 2-3 parts by weight of ethylene glycol dimethacrylate, 3-4 parts by weight of ammonium persulfate, 1.7-1.9 parts by weight of dodecyl mercaptan, glacial acetic acid, 4.4-4.6 parts by weight of nonylphenol polyoxyethylene ether, 1.1-1.3 parts by weight of triethyl phosphate, 320 parts by weight of deionized water, 17-19 parts by weight of triethanolamine, and 0.3 parts by weight of sodium bisulfite.
2. The coating thickener based on pentaerythritol triallyl ether according to claim 1, characterized in that: The pentaerythritol triallyl ether four-stage water separation reaction system was prepared by the following method: First stage: 250 parts by weight of pentaerythritol are added to the reactor, followed by 525 parts by weight of 50% sodium hydroxide solution, 11 parts by weight of tetrabutylammonium bromide catalyst, and 23 parts by weight of dimethyl sulfoxide. The temperature is raised to 100°C and maintained for 30 minutes. The temperature of the reaction system is controlled at 95-100°C. Without water separation, 465 parts by weight of allyl chloride are added dropwise within 5 hours. Second stage: 2403 parts by weight of 50% caustic soda solution and 50 parts by weight of tetrabutylammonium bromide catalyst were added to the reaction vessel. The temperature of the reaction system was controlled at 95-100℃. After adding 857 parts by weight of allyl chloride, water separation began until another 1271 parts by weight of allyl chloride was added. The total time for adding the above allyl chloride was 10 hours. Third stage: 1169 parts by weight of 50% caustic soda solution and 37 parts by weight of tetrabutylammonium bromide catalyst are added to the reaction vessel. The temperature of the reaction system is controlled at 90-100℃. Under the condition of continuous water separation, 1950 parts by weight of allyl chloride are added dropwise within 11 hours. Fourth stage: 187 parts by weight of 50% sodium hydroxide solution and 5 parts by weight of tetrabutylammonium bromide catalyst were added to the reactor. The temperature of the reaction system was controlled at 90-100℃. Under continuous water separation, 318 parts by weight of allyl chloride were added dropwise within 2 hours. The molar fraction of pentaerythritol triallyl ether in the reaction product was detected to be 82%. The temperature was maintained at 85-90℃ to obtain the four-stage water separation reaction system of pentaerythritol triallyl ether.
3. The coating thickener based on pentaerythritol triallyl ether according to claim 2, characterized in that: A method for preparing a coating thickener through in-situ copolymerization modification of a pentaerythritol triallyl ether four-stage dehydration reaction system includes the following steps: S1.1 After the fourth stage reaction, turn on the vacuum system of the reactor and control the vacuum degree to -0.08~-0.09MPa and the temperature to 85~90℃, and remove light weights under reduced pressure for 30 minutes; then slowly add glacial acetic acid dropwise to the pentaerythritol triallyl ether four-stage water separation reaction system while stirring, and adjust the pH of the pentaerythritol triallyl ether four-stage water separation reaction system to 7~8; then introduce high-purity nitrogen into the reactor and perform gas phase replacement for 20 minutes; then insert the nitrogen delivery tube into the bottom of the liquid phase and bubble the liquid phase to remove oxygen for 30 minutes, with the bubbling rate controlled at 5~8L / min, while adding 0.3 parts by weight of sodium bisulfite; then maintain a slightly positive pressure nitrogen atmosphere in the reactor until the reaction is completed; S1.
2. Mix 75 parts by weight of polyethylene glycol methyl methacrylate, 55 parts by weight of acrylic acid, 15 parts by weight of dodecyl acrylate, and 2.5 parts by weight of ethylene glycol dimethacrylate, and stir evenly to obtain a modified monomer mixture. S1.
3. Dissolve 4 parts by weight of ammonium persulfate in 60 parts by weight of deionized water to prepare an initiator solution; S1.4 At 90-95℃, add 4.5 parts by weight of nonylphenol polyoxyethylene ether, 1.2 parts by weight of triethyl phosphate, and 80% dodecyl mercaptan (all by weight of the added dodecyl mercaptan) to the pentaerythritol triallyl ether four-stage water separation reaction system treated in step S1. Stir to form a stable aqueous emulsion system. At the same time, add the modified monomer mixture and initiator solution dropwise over 5 hours. After 2 hours of dropwise addition, add the remaining dodecyl mercaptan. After the dropwise addition is completed, add 0.5 parts by weight of ammonium persulfate aqueous solution to the reaction system and keep it at 90℃ for 3 hours. Reduce the temperature of the reaction system to 50℃, add 18 parts by weight of triethanolamine, and then slowly add 260 parts by weight of deionized water. After stirring for 1 hour, filter to obtain the liquid coating thickener.
4. The coating thickener based on pentaerythritol triallyl ether according to claim 1, characterized in that: The average molecular weight of the polyethylene glycol methyl methacrylate is 950-1000.
5. A coating using a coating thickener based on pentaerythritol triallyl ether as described in any one of claims 1-4, characterized in that: Includes component A and component B; Component A comprises the following components in parts by weight: 100 parts isocyanate-modified epoxy emulsion, 75-80 parts pigments and fillers, 0.5-1 parts dispersant, 0.2-0.3 parts defoamer, 3-5 parts film-forming agent, 1.4-1.5 parts pentaerythritol triallyl ether-based paint thickener, 30 parts deionized water, and pH adjuster; Component B is a curing agent adapted to isocyanate epoxy emulsion.
6. The coating according to claim 5, characterized in that: The amount of component B added is 40% of the mass of the isocyanate-modified epoxy emulsion.
7. The coating according to claim 5, characterized in that: Component B, when calculated separately, comprises the following components in parts by weight: 80-85 parts of an amine adduct type waterborne epoxy curing agent with an amine value of 200 mg KOH / g, 5-8 parts of ethylene glycol butyl ether acetate, 2-3 parts of γ-aminopropyltriethoxysilane coupling agent, and 5-7 parts of deionized water.
8. The coating according to claim 5, characterized in that: Independently calculated, the pigments and fillers comprise the following components in parts by weight: 25 parts titanium dioxide, 15 parts zinc phosphate, 10 parts aluminum tripolyphosphate, 10 parts talc, and 5 parts precipitated barium sulfate; the dispersant is a polycarboxylate-type polymeric dispersant; the defoamer is an organosilicon polyether composite high-temperature defoamer; the film-forming agent comprises dodecyl alcohol ester and propylene glycol butyl ether in a mass ratio of 3:1; and the pH adjuster is AMP-95 pH adjuster.
9. The coating according to claim 5, characterized in that: The isocyanate-modified epoxy emulsion was prepared by the following method, by weight: 40 parts of epoxy resin E-44, 15 parts of isophorone diisocyanate, and 0.05 parts of dibutyltin dilaurate were added to a reactor, and the mixture was heated to 80°C under nitrogen protection and reacted at a constant temperature for 2 hours; then 8 parts of polyethylene glycol monomethyl ether MPEG-400 and 3 parts of dimethylolpropionic acid were added to the reactor, and the reaction was continued at 80°C for 3 hours. The reaction system was then cooled to 45°C, and 2.5 parts of triethylamine were added. After stirring for 15 minutes, 120 parts of deionized water were slowly added dropwise to the reactor under high-speed shear conditions, and emulsification was carried out for 30 minutes. Subsequently, the temperature was raised to 50°C, and 0.8 parts of ethylenediamine were added to react for 1 hour. After the reaction was completed, the temperature was lowered to below 30°C, and the mixture was filtered to obtain the isocyanate epoxy emulsion.
10. The coating according to claim 5, characterized in that: It is prepared by the following method: S1. Preparation of component A: After mixing deionized water, dispersant and defoamer evenly, slowly add pigments and fillers under stirring. After the addition is complete, adjust the stirring speed to 1200 r / min and disperse at high speed for 20 minutes. Then reduce the stirring speed to 600 r / min, maintain the stirring speed, and add isocyanate modified epoxy emulsion, film-forming agent, and pentaerythritol triallyl ether-based coating thickener in sequence. After the addition is complete, continue stirring for 10-12 minutes, and then add AMP-95 pH adjuster dropwise while stirring to adjust the pH value of component A system to 7-8. Continue stirring for 5 minutes to obtain component A. S2. Preparation of Component B: Add amine adduct type waterborne epoxy curing agent, ethylene glycol butyl ether acetate, γ-aminopropyltriethoxysilane coupling agent, and deionized water to a mixing container in sequence. Stir at 800 r / min for 8-10 minutes at room temperature to obtain component B. After the preparation of components A and B is completed, store them separately. Mix them in proportion before use and stir evenly to obtain the coating for application.