An antistatic epoxy resin floor coating and a preparation method thereof

Abstract

This invention relates to the field of epoxy resin floor coating technology, and discloses an antistatic epoxy resin floor coating and its preparation method. The invention involves mixing an active diluent, epoxy resin, filler, dispersant, defoamer, and leveling agent to obtain an epoxy emulsion component. A curing agent component containing a water-based epoxy curing agent and a thiol-terminated cationic rosin polymer is then added to obtain the antistatic epoxy resin floor coating. The thiol-terminated cationic rosin polymer contains thiol groups, which can react with the epoxy groups of the epoxy resin, improving the pencil hardness, abrasion resistance, corrosion resistance, and water resistance of the floor coating. The cationic rosin polymer contains quaternary ammonium salt antistatic groups, which, when introduced into the epoxy resin molecular chain, can form a conductive layer on the coating film surface, accelerating charge dissipation and reducing surface resistance, thus providing excellent antistatic properties.

Description

Technical Field

[0001] This invention relates to the field of epoxy resin floor coating technology, specifically to an antistatic epoxy resin floor coating and its preparation method. Background Technology

[0002] Epoxy resin coatings possess excellent adhesion, weather resistance, and mechanical strength, making them widely used in floor coatings, metal corrosion protection, and electronic applications. However, special locations such as flammable and explosive environments, semiconductor and microelectronics factories, and textile mills require anti-static flooring to ensure environmental safety and equipment stability. Epoxy resin floor coatings, however, have poor anti-static properties, limiting their application areas.

[0003] Adding antistatic agents to epoxy resin floor coatings can effectively improve their antistatic properties. Common antistatic agents include conductive carbon black and graphene. However, conductive carbon black requires a large amount, which significantly affects the coating's performance, while graphene is expensive and difficult to commercialize. Quaternary ammonium salt cationic antistatic agents have diverse preparation methods, excellent compatibility with polymer materials, and important applications in coatings, films, pipes, and rubber. Summary of the Invention

[0004] (a) Technical problem solved: The present invention solves the problem of poor antistatic properties of epoxy resin floor coatings.

[0005] (II) Technical Solution: A method for preparing an antistatic epoxy resin floor coating:

[0006] (1) Add reactive diluent, epoxy resin, filler, dispersant, defoamer and leveling agent to the container, stir and mix well to obtain epoxy emulsion components.

[0007] (2) Add water, water-based epoxy curing agent, and thiol-terminated cationic rosin polymer to the container, stir and mix well to obtain curing agent component; then add curing agent component to epoxy emulsion component, stir and mix well to obtain antistatic epoxy resin floor coating.

[0008] Preferably, the mass ratio of reactive diluent, epoxy resin, filler, dispersant, defoamer, leveling agent, water, waterborne epoxy curing agent, and thiol-terminated cationic rosin polymer is (12-20):100:(65-80):(1.2-2):(0.6-1):(0.5-0.8):(10-18):(32-46):(8-20).

[0009] Preferably, the active diluent is butyl glycidyl ether, ethylene glycol diglycidyl ether, or neopentyl glycol diglycidyl ether.

[0010] Preferably, the filler includes any one or a combination of silica powder, quartz powder, calcium carbonate, barium sulfate, and talc.

[0011] Preferred method for preparing thiol-terminated cationic rosin polymer:

[0012] (1) Add toluene solvent, rosin acid, 2-chloroethanol and p-toluenesulfonic acid in a molar ratio of 1:(1.4-2):(0.2-0.3) to the reaction vessel, heat to 80-100℃, react for 10-18h, then distill under reduced pressure, and recrystallize the product in dichloromethane to obtain chloroacetic acid rosin.

[0013] (2) Add N,N-dimethylacetamide solvent, N-methyldiallylamine, ethylene glycol dimercaptoacetate, and triethylamine to the reaction vessel and stir at 15-25℃ for 2-3 h. Then add chloroacetic acid rosin, wherein the molar ratio of N-methyldiallylamine, ethylene glycol dimercaptoacetate, triethylamine, and chloroacetic acid rosin is 1:(1.1-1.2):(0.012-0.016):(0.4-1.2). Purge with nitrogen gas, heat to 80-110℃, stir and react for 24-48 h. Pour the solution into ethanol, stir and filter. Wash the precipitate with ethanol and dry to obtain the terminal mercapto cationic rosin polymer.

[0014] (III) Beneficial technical effects: The present invention involves the polymerization of N-methyldiallylamine and ethylene glycol dimercaptoacetate into mercapto-olefins, followed by a quaternization reaction with chloroacetic acid rosin to obtain a mercapto-terminated cationic rosin polymer, which is then blended with epoxy resin, waterborne epoxy curing agent Evonik WH-1000, etc., to obtain an antistatic epoxy resin floor coating.

[0015] The thiol-terminated cationic rosin polymer of the present invention contains thiol groups, which can react with the epoxy groups of epoxy resin, thereby bonding the cationic rosin polymer into the epoxy resin curing system. The rosin contains rigid and stable fused ring bonds and is highly hydrophobic. When introduced into the epoxy resin molecular chain, it can improve the pencil hardness, abrasion resistance, corrosion resistance and water resistance of the floor coating.

[0016] The cationic rosin polymer of the present invention contains quaternary ammonium salt antistatic groups, which are introduced into the epoxy resin molecular chain to form a conductive layer on the surface of the coating film, accelerate charge dissipation, reduce surface resistance, and play a good antistatic role. Detailed Implementation

[0017] Example 1

[0018] (1) Add 0.8 L toluene solvent, 0.3 mol rosin acid, 0.42 mol 2-chloroethanol, and 0.09 mol p-toluenesulfonic acid to a reaction vessel, heat to 80 °C, react for 18 h, then distill under reduced pressure. Recrystallize the product in dichloromethane to obtain chloroacetic acid rosin. The preparation reaction formula is as follows:

[0019] .

[0020] (2) Add 1.2 L N,N-dimethylacetamide solvent, 0.5 mol N-methyldiallylamine, 0.55 mol ethylene glycol dimercaptoacetate, and 7.2 mmol triethylamine to a reaction vessel. Stir the mixture at 25 °C for 2 h. Then add 0.35 mol chloroacetic acid rosin, purge with nitrogen, heat to 110 °C, and stir for 24 h. Pour the solution into ethanol, stir, filter, wash the precipitate with ethanol, and dry to obtain a thiol-terminated cationic rosin polymer. The preparation reaction formula is as follows:

[0021] .

[0022] (3) Add 200g butyl glycidyl ether, 1kg epoxy resin E51, 460g silica powder, 260g talc powder, 15g dispersant Dispex CX 4320AM, 10g defoamer Dow Corning AFE-1247, and 7g leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain epoxy emulsion components.

[0023] (4) Add 180g of water, 460g of waterborne epoxy curing agent Evonik WH-1000, and 80g of thiol-terminated cationic rosin polymer to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain the antistatic epoxy resin floor coating.

[0024] Example 2

[0025] (1) Add 1L of toluene solvent, 0.3mol of rosin acid, 0.6mol of 2-chloroethanol and 0.06mol of p-toluenesulfonic acid to the reaction vessel, heat to 100℃ and react for 10h. During the reaction, reflux is condensed and then distilled under reduced pressure. The product is recrystallized in dichloromethane to obtain chloroacetic acid rosin.

[0026] (2) Add 1.5 L N,N-dimethylacetamide solvent, 0.5 mol N-methyldiallylamine, 0.6 mol ethylene glycol dimercaptoacetate and 8 mmol triethylamine to the reaction vessel, stir and react at 15 °C for 3 h, then add 0.2 mol chloroacetic acid rosin, purge with nitrogen, heat to 100 °C, stir and react for 48 h, pour the solution into ethanol, stir and filter, wash the precipitate with ethanol, dry, and obtain terminal mercapto cationic rosin polymer.

[0027] (3) Add 120g of ethylene glycol diglycidyl ether, 1kg of epoxy resin E51, 490g of silica powder, 270g of barium sulfate, 12g of dispersant Dispex CX 4320AM, 10g of defoamer Dow Corning AFE-1247, and 7g of leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain the epoxy emulsion component.

[0028] (4) Add 160g of water, 420g of waterborne epoxy curing agent Evonik WH-1000, and 120g of thiol-terminated cationic rosin polymer to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain the antistatic epoxy resin floor coating.

[0029] Example 3

[0030] (1) Add 1.5 L N,N-dimethylacetamide solvent, 0.5 mol N-methyldiallylamine, 0.58 mol ethylene glycol dimercaptoacetate and 6 mmol triethylamine to the reaction vessel, stir and react at 25 °C for 2 h, then add 0.6 mol chloroacetic acid rosin (prepared from Example 1), purge with nitrogen, heat to 80 °C, stir and react for 48 h, pour the solution into ethanol, stir and filter, wash the precipitate with ethanol, dry, and obtain terminal mercapto cationic rosin polymer.

[0031] (2) Add 200g butyl glycidyl ether, 1kg epoxy resin E51, 570g quartz powder, 230g talc powder, 20g dispersant Dispex CX 4320AM, 9g defoamer Dow Corning AFE-1247, and 5g leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain epoxy emulsion components.

[0032] (3) Add 140g of water, 370g of waterborne epoxy curing agent Evonik WH-1000, and 160g of thiol-terminated cationic rosin polymer to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain the antistatic epoxy resin floor coating.

[0033] Example 4

[0034] (1) Add 1.4 L N,N-dimethylacetamide solvent, 0.5 mol N-methyldiallylamine, 0.6 mol ethylene glycol dimercaptoacetate and 6.4 mmol triethylamine to the reaction vessel and stir at 20 °C for 3 h. Then add 0.5 mol chloroacetate rosin (prepared from Example 1), purge with nitrogen, heat to 100 °C and stir for 36 h. Pour the solution into ethanol, stir and filter. Wash the precipitate with ethanol and dry to obtain the terminal mercapto cationic rosin polymer.

[0035] (2) Add 136g neopentyl glycol diglycidyl ether, 1kg epoxy resin E51, 430g silica powder, 220g calcium carbonate, 17g dispersant Dispex CX 4320AM, 6g defoamer Dow Corning AFE-1247, and 8g leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain epoxy emulsion components.

[0036] (3) Add 100g of water, 320g of waterborne epoxy curing agent Evonik WH-1000, and 200g of thiol-terminated cationic rosin polymer to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain the antistatic epoxy resin floor coating.

[0037] Comparative Example 1

[0038] (1) Add 200g butyl glycidyl ether, 1kg epoxy resin E51, 460g silica powder, 260g talc powder, 15g dispersant Dispex CX 4320AM, 10g defoamer Dow Corning AFE-1247, and 7g leveling agent Shengsheng SSL-311 to a container, stir and mix well to obtain epoxy emulsion components.

[0039] (2) Add 180g of water and 460g of waterborne epoxy curing agent Evonik WH-1000 to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain epoxy resin floor coating.

[0040] Comparative Example 2

[0041] (1) Add 1.2 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyldiallylamine, 0.55 mol of ethylene glycol dimercaptoacetate and 7.2 mmol of triethylamine to the reaction vessel, stir and react at 25 °C for 2 h, remove N,N-dimethylacetamide by vacuum distillation, wash with petroleum ether and dry to obtain the terminal mercapto polymer.

[0042] (2) Add 200g butyl glycidyl ether, 1kg epoxy resin E51, 460g silica powder, 260g talc powder, 15g dispersant Dispex CX 4320AM, 10g defoamer Dow Corning AFE-1247, and 7g leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain epoxy emulsion components.

[0043] (3) Add 180g of water, 460g of waterborne epoxy curing agent Evonik WH-1000 and 80g of end-thiol polymer to the container, stir and mix well to obtain the curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix well to obtain epoxy resin floor coating.

[0044] Comparative Example 3

[0045] (1) Add 1.2 L N,N-dimethylacetamide solvent, 0.5 mol N-methyldiallylamine, 0.55 mol ethylene glycol dimercaptoacetate and 7.2 mmol triethylamine to the reaction vessel, stir at 25 °C for 2 h, then add 0.35 mol ethyl chloroacetate, purge with nitrogen, heat to 110 °C, stir for 24 h, pour the solution into ethanol, stir and filter, wash the precipitate with ethanol, dry, and obtain the terminal thiol cationic polymer.

[0046] (2) Add 200g butyl glycidyl ether, 1kg epoxy resin E51, 460g silica powder, 260g talc powder, 15g dispersant Dispex CX 4320AM, 10g defoamer Dow Corning AFE-1247, and 7g leveling agent Shengsheng SSL-311 to the container, stir and mix well to obtain epoxy emulsion components.

[0047] (3) Add 180g of water, 460g of waterborne epoxy curing agent Evonik WH-1000 and 80g of terminal thiol cationic polymer to the container, stir and mix well to obtain curing agent component; then add curing agent component to epoxy emulsion component, stir and mix well to obtain epoxy resin floor coating.

[0048] The performance of the floor coating film was tested according to standard SJ / T 11294-2018. The results are shown in Table 1.

[0049] Table 1 Performance Tests of Epoxy Resin Floor Coatings

[0050] Group Point-to-point resistance (Ω) Pencil hardness Abrasion resistance (g) Corrosion resistance (20% sodium hydroxide solution, 144h) Water resistance (360h) Example 1 <![CDATA[4.78×10 7 ]]> 4H 0.033 No bubbling, no peeling No bubbling, no peeling Example 2 <![CDATA[9.13×10 6 ]]> 3H 0.037 No bubbling, no peeling No bubbling, no peeling Example 3 <![CDATA[6.25×10 5 ]]> 5H 0.018 No bubbling, no peeling No bubbling, no peeling Example 4 <![CDATA[1.06×10 5 ]]> 3H 0.026 It bubbles but doesn't peel off. No bubbling, no peeling Comparative Example 1 <![CDATA[8.31×10 11 ]]> 3H 0.047 Bubbling, peeling It bubbles but doesn't peel off. Comparative Example 2 <![CDATA[8.70×10 11 ]]> 3H 0.044 Bubbling, peeling No bubbling, no peeling Comparative Example 3 <![CDATA[4.49×10 7 ]]> 3H 0.042 Bubbling, peeling Bubbling, peeling

[0051] Compared with Comparative Examples 1-3, the epoxy resin floor coatings of Examples 1-4 contain terminal thiol cationic rosin polymers. These thiol groups can react with the epoxy groups of epoxy resin, thereby bonding the cationic rosin polymers into the epoxy resin curing system. Rosin contains rigid and stable fused ring bonds and is highly hydrophobic. Introducing it into the epoxy resin molecular chain can improve the pencil hardness, abrasion resistance, corrosion resistance, and water resistance of the floor coating. At the same time, the cationic rosin polymers contain quaternary ammonium salt antistatic groups, which can form a conductive layer on the surface of the coating film, accelerate charge dissipation, and help reduce surface resistance, thus playing a good antistatic role.

Claims

1. A method for preparing an antistatic epoxy resin floor coating, characterized in that, The preparation method includes the following steps: (1) Add reactive diluent, epoxy resin, filler, dispersant, defoamer and leveling agent to the container, stir and mix well to obtain epoxy emulsion components; (2) Add water, water-based epoxy curing agent, and mercapto-terminated cationic rosin polymer to the container, stir and mix well to obtain curing agent component; then add curing agent component to epoxy emulsion component, stir and mix well to obtain antistatic epoxy resin floor coating. The preparation method of the terminal thiol cationic rosin polymer: (1) Toluene solvent, rosin acid, 2-chloroethanol and p-toluenesulfonic acid were added to the reaction vessel. After the reaction, the product was distilled under reduced pressure and recrystallized to obtain chloroacetic acid rosin. (2) Add N,N-dimethylacetamide solvent, N-methyldiallylamine, ethylene glycol dimercaptoacetate and triethylamine to the reaction vessel, stir and react at 15-25℃ for 2-3h, then add chloroacetic acid rosin, purge with nitrogen, heat to 80-110℃, stir and react for 24-48h, pour the solution into ethanol, stir and filter, wash the precipitate, dry, and obtain terminal mercapto cationic rosin polymer; The molar ratio of rosin acid, 2-chloroethanol, and p-toluenesulfonic acid in (1) is 1:(1.4-2):(0.2-0.3). The molar ratio of N-methyldiallylamine, ethylene glycol dimercaptoacetate, triethylamine, and chloroacetic acid rosin in (2) is 1:(1.1-1.2):(0.012-0.016):(0.4-1.2).

2. The method for preparing antistatic epoxy resin floor coating according to claim 1, characterized in that, The mass ratio of the reactive diluent, epoxy resin, filler, dispersant, defoamer, leveling agent, water, waterborne epoxy curing agent, and terminal thiol cationic rosin polymer is (12-20):100:(65-80):(1.2-2):(0.6-1):(0.5-0.8):(10-18):(32-46):(8-20).

3. The method for preparing antistatic epoxy resin floor coating according to claim 2, characterized in that, The active diluent is butyl glycidyl ether, ethylene glycol diglycidyl ether, or neopentyl glycol diglycidyl ether.

4. The method for preparing antistatic epoxy resin floor coating according to claim 2, characterized in that, The filler includes any one or a combination of silica powder, quartz powder, calcium carbonate, barium sulfate, and talc.

5. The method for preparing the antistatic epoxy resin floor coating according to claim 1, characterized in that, The reaction temperature in (1) is 80-100℃ and the reaction time is 10-18h.

6. An antistatic epoxy resin floor coating obtained by the preparation method according to any one of claims 1-5.