Anti-freezing heat-resistant mucilage-based slurry composite material and preparation method thereof

Abstract

The invention relates to the technical field of coatings, and discloses an anti-freezing heat-resistant mucilage-based slurry composite material and a preparation method thereof.The composite material is prepared by firstly preparing a polymer seed solution and then polymerizing a phenyl sulfone cross-linking agent and a polymeric anti-freezing monomer onto seeds, the phenyl sulfone cross-linking agent structure contains a sulfone structure, and the polymeric anti-freezing monomer contains a polymer structure; the structural stability of the acrylate emulsion can be improved, the crosslinking density of an acrylate molecular chain is improved after crosslinking, and the movement of the molecular chain is blocked, so that the acrylate emulsion can be kept stable under a high-temperature condition, and the polymeric anti-freezing monomer can be polymerized into the molecular chain of the emulsion polymer, on one hand, the polymeric anti-freezing monomer has a lower freezing point; on one hand, the freezing point of water in the base slurry can be reduced, the anti-freezing performance of the base slurry can be improved, on the other hand, a large number of hydrophilic ether bonds are contained in the structure and can form strong hydrogen bonds with water, formation and growth of ice crystals are interfered, and therefore the anti-freezing performance of the base slurry is greatly improved.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to an antifreeze and heat-resistant adhesive-based composite material and its preparation method. Background Technology

[0002] Paint is a material applied to the surface of an object to form a firmly adhering, continuous film, and is an indispensable basic material in modern society. Its core functions are decoration, protection, and imparting specific special functions to the coated object. Traditional paint technology has long revolved around several major systems. First, solvent-based paints: using organic solvents as the dispersion medium, the film-forming substance forms a dense paint film after the solvent evaporates. These paints have advantages such as good film-forming properties, high hardness, and strong chemical resistance, but they release large amounts of volatile organic compounds during production and use, posing a threat to the environment and human health. Second, water-based paints: using water as the main dispersion medium, this is currently the mainstream direction for the development of environmentally friendly paints. Its core technology lies in using emulsification and dispersion methods to stably exist hydrophobic resins in water. Water-based paints significantly reduce VOC emissions; however, they lag behind solvent-based paints in terms of heat resistance and freeze resistance.

[0003] With the continuous development of coating technology, the application environment of coatings is becoming increasingly demanding. Water-based coatings often face core problems such as freeze-thaw damage and deterioration of application performance in low-temperature construction scenarios. Traditional low-molecular-weight antifreeze agents such as ethylene glycol and propylene glycol are volatile organic compounds, which cannot guarantee the long-term antifreeze performance of coatings. In high-temperature environments, they may soften. This results in a limited application range for water-based coatings, which cannot meet the current needs of coating applications. Based on this, the present invention provides a freeze-thaw and heat-resistant coating base slurry that can solve the problems existing in the prior art. Summary of the Invention

[0004] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide an antifreeze and heat-resistant adhesive base slurry composite material and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions: A freeze-thaw resistant and heat-resistant adhesive-based composite material, comprising the following raw materials measured in parts by weight: 25-35 parts methyl acrylate, 10-15 parts butyl acrylate, 3-5 parts methyl methacrylate, 2-4 parts butyl methacrylate, 10-20 parts isooctyl acrylate, 0.5-1.5 parts methacrylic acid, 0.5-1 part sulfone crosslinking agent, 1-2 parts polymeric antifreeze monomer, 0.5-1 part emulsifier, 0.3-0.6 parts initiator one, 0.05-0.1 parts initiator two, 0.05-0.15 parts defoamer, and 100-120 parts deionized water.

[0006] As a further aspect of the present invention, the sulfone crosslinking agent is prepared by the following method: Step 1: Add sulfamic acid, diglycidyl cyclohexane-1,2-dicarboxylic acid and N,N-dimethylformamide to a nitrogen-filled polymerization reactor, start stirring, mix evenly, raise the temperature to 70-80℃, and continue stirring for 6-12 hours to obtain the intermediate. Step 2: Add the capping agent to the intermediate, continue stirring for 1-2 hours, remove the nitrogen gas, evaporate the solvent, collect the crude product, and obtain the sulfone crosslinking agent through purification process.

[0007] As a further aspect of the present invention, in step one, the molar ratio of sulfamic acid and cyclohexane-1,2-dicarboxylic acid diglycidyl ester is 1:0.9-0.95.

[0008] As a further aspect of the present invention, in step two, the capping agent is glycidyl methacrylate or 2,3-epoxypropyl acrylate.

[0009] It should be noted that in the above technical solution, sulfone and cyclohexane-1,2-dicarboxylic acid diglycidyl ester are first used as raw materials. The amino and epoxy groups in their structures can undergo a continuous ring-opening reaction under high temperature conditions to obtain an intermediate with an alternating sulfone-cyclohexane linkage structure. By controlling the amount of sulfone and cyclohexane-1,2-dicarboxylic acid diglycidyl ester, the obtained intermediate can be made to be amino-terminated. By using a terminating agent to terminate the amino group, a sulfone crosslinking agent with unsaturated alkenyl substituents at the end of the structure is obtained.

[0010] As a further aspect of the present invention, the polymeric antifreeze monomer is prepared by the following method: Polyethylene oxide was added to acetone and stirred until homogeneous. Then, alkenylating reagent and composite catalyst were added. After the addition was complete, the mixture was mechanically stirred at room temperature for 4-6 hours. The solvent was evaporated to remove the solvent, and the crude product was collected and purified to obtain the polymeric antifreeze monomer.

[0011] As a further embodiment of the present invention, the alkenylating agent is 6-maleimide hexanoic acid or 3-maleimide propionic acid.

[0012] As a further embodiment of the present invention, the composite catalyst is a mixture of dicyclohexylcarbodiimide and 4-dimethylaminopyridine in a mass ratio of 1:0.2-0.3.

[0013] In the above technical solution, a composite catalyst is used to catalyze the condensation reaction between the hydroxyl groups of polyethylene oxide and the carboxyl groups of the alkenylating agent to obtain polyethylene oxide containing unsaturated alkenyl substituents in its structure, i.e., a polymeric antifreeze monomer.

[0014] As a further embodiment of the present invention, the emulsifier is sodium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate.

[0015] As a further embodiment of the present invention, the first initiator is azobisisobutyronitrile or benzoyl peroxide; the second initiator is any one of potassium persulfate, sodium persulfate or ammonium persulfate.

[0016] A method for preparing an antifreeze and heat-resistant adhesive-based composite material includes the following steps: Step 1: Add one-third of the emulsifier to four-fifths of the deionized water and stir to mix to form an emulsion; The second step involves mixing methyl acrylate, butyl acrylate, methacrylic acid, and initiator to form a core-layer polymerization monomer liquid. This liquid is then added to an emulsion and subjected to high-speed homogenization emulsification to form a micro-suspension. Under nitrogen protection, the temperature is raised to 70-80℃ and stirred continuously for 3-6 hours to form a core-layer polymerization liquid. Step 3: Add methyl methacrylate, butyl methacrylate, isooctyl acrylate, sulfone crosslinking agent, polymeric antifreeze monomer, initiator II, the remaining emulsifier, and the remaining deionized water to a mixer, stir and emulsify to form a shell monomer liquid. Step 4: Add the shell monomer liquid to the core polymerization liquid, then raise the temperature to 85-90℃ and keep it warm for 4-8 hours. Then stop heating and wait for it to cool to room temperature. Add the defoamer, stir for 10-20 minutes, let it stand to defoam, and then discharge the material.

[0017] The beneficial effects of this invention are: (1) The present invention first prepares a polymer seed liquid, and then polymerizes sulfone crosslinking agent and polymeric antifreeze monomer onto the seed to obtain an acrylate paste base with a shell-core structure. On the one hand, the sulfone crosslinking agent contains a sulfone structure, which can improve the structural stability of the acrylate emulsion. Moreover, after crosslinking, the crosslinking density of the acrylate molecular chain increases and a network structure is established, which in turn hinders the movement of the molecular chain. Therefore, it can remain stable under high temperature conditions and exhibit good heat resistance.

[0018] (2) The polymeric antifreeze monomer prepared by the present invention can be polymerized into the emulsion polymer molecular chain. On the one hand, it has a low freezing point, which can reduce the freezing point of water in the base slurry and improve the antifreeze performance of the base slurry. On the other hand, its structure contains a large number of hydrophilic ether bonds, which can form strong hydrogen bonds with water, interfere with the formation and growth of ice crystals, thereby greatly improving the antifreeze performance of the base slurry.

[0019] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Detailed Implementation

[0020] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Preparation Example 1 Preparation of sulfone crosslinking agent: Step 1: Add 0.4g of sulfamic acid, 0.42g of cyclohexane-1,2-dicarboxylic acid diglycidyl ester and N,N-dimethylformamide to a nitrogen-filled polymerization reactor. Start stirring and mix evenly. Then raise the temperature to 75℃ and keep stirring at this temperature for 9 hours to obtain the intermediate. Step 2: Add 0.1g of glycidyl methacrylate to the intermediate, continue stirring for 1 hour, remove nitrogen, evaporate to remove solvent, collect crude product, and obtain sulfone crosslinking agent through purification process.

[0022] Preparation Example 2 Preparation of polymeric antifreeze monomers: 1.2 g of polyethylene oxide was added to acetone and stirred until homogeneous. Then, 0.2 g of 6-maleimide hexanoic acid, 0.1 g of dicyclohexylcarbodiimide, and 0.03 g of 4-dimethylaminopyridine were added. After the addition was complete, the mixture was mechanically stirred at room temperature for 4 h. The solvent was evaporated to remove the solvent, and the crude product was collected and purified to obtain a polymeric antifreeze monomer.

[0023] Example 1 A freeze-thaw resistant and heat-resistant adhesive-based composite material, comprising the following raw materials measured in parts by weight: 25 parts methyl acrylate, 10 parts butyl acrylate, 3 parts methyl methacrylate, 2 parts butyl methacrylate, 10 parts isooctyl acrylate, 0.5 parts methacrylic acid, 0.5 parts sulfone crosslinking agent, 1 part polymeric antifreeze monomer, 0.5 parts emulsifier, 0.3 parts initiator one, 0.05 parts initiator two, 0.05 parts defoamer, 100 parts deionized water; The preparation method of the base slurry composite material includes the following steps: Step 1: Add one-third of the emulsifier to four-fifths of the deionized water and stir to mix to form an emulsion; The second step involves mixing methyl acrylate, butyl acrylate, methacrylic acid, and initiator to form a core-layer polymerization monomer liquid. This liquid is then added to an emulsion and subjected to high-speed homogenization emulsification to form a micro-suspension. Under nitrogen protection, the temperature is raised to 75°C and stirred continuously for 4 hours to form a core-layer polymerization liquid. Step 3: Add methyl methacrylate, butyl methacrylate, isooctyl acrylate, sulfone crosslinking agent, polymeric antifreeze monomer, initiator II, the remaining emulsifier, and the remaining deionized water to a mixer, stir and emulsify to form a shell monomer liquid. Step 4: Add the shell monomer liquid to the core polymerization liquid, then raise the temperature to 85°C and keep it at that temperature for 6 hours. Then stop heating and let it cool to room temperature. Add the defoamer, stir for 15 minutes, let it stand to defoam, and then discharge the material.

[0024] The preparation method of the sulfone crosslinking agent is shown in Preparation Example 1; the preparation method of the polymeric antifreeze monomer is shown in Preparation Example 2; the emulsifier is sodium dodecylbenzenesulfonate; the initiator one is azobisisobutyronitrile; the initiator two is potassium persulfate; the defoamer is BYK-065; the following are all the same.

[0025] Example 2 A freeze-thaw resistant and heat-resistant adhesive-based composite material, comprising the following raw materials measured in parts by weight: 28 parts methyl acrylate, 12 parts butyl acrylate, 4 parts methyl methacrylate, 3 parts butyl methacrylate, 12 parts isooctyl acrylate, 1 part methacrylic acid, 0.8 parts sulfone crosslinking agent, 1.8 parts polymeric antifreeze monomer, 0.8 parts emulsifier, 0.4 parts initiator one, 0.06 parts initiator two, 0.1 parts defoamer, and 110 parts deionized water; The preparation method of the base slurry composite material includes the following steps: Step 1: Add one-third of the emulsifier to four-fifths of the deionized water and stir to mix to form an emulsion; The second step involves mixing methyl acrylate, butyl acrylate, methacrylic acid, and initiator to form a core-layer polymerization monomer liquid. This liquid is then added to an emulsion and subjected to high-speed homogenization emulsification to form a micro-suspension. Under nitrogen protection, the temperature is raised to 75°C and stirred continuously for 4 hours to form a core-layer polymerization liquid. Step 3: Add methyl methacrylate, butyl methacrylate, isooctyl acrylate, sulfone crosslinking agent, polymeric antifreeze monomer, initiator II, the remaining emulsifier, and the remaining deionized water to a mixer, stir and emulsify to form a shell monomer liquid. Step 4: Add the shell monomer liquid to the core polymerization liquid, then raise the temperature to 85°C and keep it at that temperature for 6 hours. Then stop heating and let it cool to room temperature. Add the defoamer, stir for 15 minutes, let it stand to defoam, and then discharge the material.

[0026] Example 3 A freeze-thaw resistant and heat-resistant adhesive-based composite material, comprising the following raw materials measured in parts by weight: 35 parts methyl acrylate, 15 parts butyl acrylate, 5 parts methyl methacrylate, 4 parts butyl methacrylate, 20 parts isooctyl acrylate, 1.5 parts methacrylic acid, 1 part sulfone crosslinking agent, 2 parts polymeric antifreeze monomer, 1 part emulsifier, 0.6 parts initiator one, 0.1 parts initiator two, 0.15 parts defoamer, and 120 parts deionized water; The preparation method of the base slurry composite material includes the following steps: Step 1: Add one-third of the emulsifier to four-fifths of the deionized water and stir to mix to form an emulsion; The second step involves mixing methyl acrylate, butyl acrylate, methacrylic acid, and initiator to form a core-layer polymerization monomer liquid. This liquid is then added to an emulsion and subjected to high-speed homogenization emulsification to form a micro-suspension. Under nitrogen protection, the temperature is raised to 75°C and stirred continuously for 4 hours to form a core-layer polymerization liquid. Step 3: Add methyl methacrylate, butyl methacrylate, isooctyl acrylate, sulfone crosslinking agent, polymeric antifreeze monomer, initiator II, the remaining emulsifier, and the remaining deionized water to a mixer, stir and emulsify to form a shell monomer liquid. Step 4: Add the shell monomer liquid to the core polymerization liquid, then raise the temperature to 85°C and keep it at that temperature for 6 hours. Then stop heating and let it cool to room temperature. Add the defoamer, stir for 15 minutes, let it stand to defoam, and then discharge the material.

[0027] Comparative Example 1 A paste-based composite material, which differs from Example 2 in that the sulfone crosslinking agent is removed, but otherwise it is the same.

[0028] Comparative Example 2 A paste-based composite material, which differs from Example 2 in that the polymeric antifreeze monomer is removed, but otherwise it is the same.

[0029] Test case a. The viscosity of the base slurry composite materials in the examples and comparative examples was tested at room temperature and after three freeze-thaw cycles at -5°C to evaluate their freeze-thaw resistance. b. Apply the base slurry composite material from the examples and comparative examples to the surface of a stainless steel plate, controlling the coating amount to be 50 g / m². 2After coating, allow it to fully cure at 100℃, then transfer it to 120℃ and keep it in the environment for 48 hours. After that, take it out, observe the coating phenomenon, and evaluate the heat resistance. Analysis and test results show that the base slurry prepared in the embodiments of the present invention has good antifreeze and heat resistance properties.

[0030] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0031] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A freeze-thaw resistant and heat-resistant adhesive-based composite material, characterized in that, Including the following raw materials measured in parts by weight: 25-35 parts methyl acrylate, 10-15 parts butyl acrylate, 3-5 parts methyl methacrylate, 2-4 parts butyl methacrylate, 10-20 parts isooctyl acrylate, 0.5-1.5 parts methacrylic acid, 0.5-1 part sulfone crosslinking agent, 1-2 parts polymeric antifreeze monomer, 0.5-1 part emulsifier, 0.3-0.6 parts initiator one, 0.05-0.1 parts initiator two, 0.05-0.15 parts defoamer, and 100-120 parts deionized water.

2. The antifreeze and heat-resistant adhesive-based composite material according to claim 1, characterized in that, The sulfone crosslinking agent is prepared by the following method: Step 1: Add sulfamic acid, diglycidyl cyclohexane-1,2-dicarboxylic acid and N,N-dimethylformamide to a nitrogen-filled polymerization reactor, start stirring, mix evenly, raise the temperature to 70-80℃, and continue stirring for 6-12 hours to obtain the intermediate. Step 2: Add the capping agent to the intermediate, continue stirring for 1-2 hours, remove the nitrogen gas, evaporate the solvent, collect the crude product, and obtain the sulfone crosslinking agent through purification process.

3. The antifreeze and heat-resistant adhesive-based composite material according to claim 2, characterized in that, In step one, the molar ratio of sulfamic acid and cyclohexane-1,2-dicarboxylic acid diglycidyl ester is 1:0.9-0.

95.

4. The antifreeze and heat-resistant adhesive-based composite material according to claim 2, characterized in that, In step two, the capping agent is glycidyl methacrylate or 2,3-epoxypropyl acrylate.

5. The antifreeze and heat-resistant adhesive-based composite material according to claim 1, characterized in that, The polymeric antifreeze monomer is prepared using the following method: Polyethylene oxide was added to acetone and stirred until homogeneous. Then, alkenylating reagent and composite catalyst were added. After the addition was complete, the mixture was mechanically stirred at room temperature for 4-6 hours. The solvent was evaporated to remove the solvent, and the crude product was collected and purified to obtain the polymeric antifreeze monomer.

6. The antifreeze and heat-resistant adhesive-based composite material according to claim 5, characterized in that, The alkenylating agent is 6-maleimide hexanoic acid or 3-maleimide propionic acid.

7. The antifreeze and heat-resistant adhesive-based composite material according to claim 5, characterized in that, The composite catalyst is a mixture of dicyclohexylcarbodiimide and 4-dimethylaminopyridine in a mass ratio of 1:0.2-0.

3.

8. The antifreeze and heat-resistant adhesive-based composite material according to claim 1, characterized in that, The emulsifier is sodium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate.

9. The antifreeze and heat-resistant adhesive-based composite material according to claim 1, characterized in that, The first initiator is azobisisobutyronitrile or benzoyl peroxide; the second initiator is any one of potassium persulfate, sodium persulfate or ammonium persulfate.

10. A method for preparing the antifreeze and heat-resistant adhesive-based composite material as described in claim 1, characterized in that, Includes the following steps: Step 1: Add one-third of the emulsifier to four-fifths of the deionized water and stir to mix to form an emulsion; The second step involves mixing methyl acrylate, butyl acrylate, methacrylic acid, and initiator to form a core-layer polymerization monomer liquid. This liquid is then added to an emulsion and subjected to high-speed homogenization emulsification to form a micro-suspension. Under nitrogen protection, the temperature is raised to 70-80℃ and stirred continuously for 3-6 hours to form a core-layer polymerization liquid. Step 3: Add methyl methacrylate, butyl methacrylate, isooctyl acrylate, sulfone crosslinking agent, polymeric antifreeze monomer, initiator II, the remaining emulsifier, and the remaining deionized water to a mixer, stir and emulsify to form a shell monomer liquid. Step 4: Add the shell monomer liquid to the core polymerization liquid, then raise the temperature to 85-90℃ and keep it warm for 4-8 hours. Then stop heating and wait for it to cool to room temperature. Add the defoamer, stir for 10-20 minutes, let it stand to defoam, and then discharge the material.

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