Anti-static epoxy resin floor coating and preparation method thereof

Abstract

The invention relates to the technical field of epoxy resin floor paint, and discloses an anti-static epoxy resin floor paint and a preparation method thereof.The preparation method comprises the steps that a reactive diluent, epoxy resin, filler, a dispersing agent, a defoaming agent and a flatting agent are mixed to be uniform, and an epoxy emulsion component is obtained; and adding a curing agent component containing a waterborne epoxy curing agent and a sulfydryl-terminated cationic rosin polymer to obtain the anti-static epoxy resin floor coating. The sulfydryl-terminated cationic rosin polymer contains a sulfydryl-terminated group which can react with an epoxy group of the epoxy resin, so that the pencil hardness, the wear resistance, the corrosion resistance and the water resistance of the floor coating can be improved. The cationic rosin polymer contains quaternary ammonium salt antistatic groups and is introduced into an epoxy resin molecular chain, a conductive layer can be formed on the surface of a paint film of the coating, charge dissipation is accelerated, surface resistance is reduced, and a good antistatic effect is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy floor paint, in particular to an anti-static epoxy floor paint and a preparation method thereof. BACKGROUND

[0002] Epoxy resin paint has good adhesion, weather resistance, mechanical strength and other characteristics, and is widely used in floor painting, metal corrosion protection, electronic appliances and other aspects. In flammable and explosive places, semiconductor microelectronic factories, textile factories and other special places, the ground is required to have anti-static function to ensure the safety of production environment and the stability of equipment. The anti-static performance of epoxy floor paint is poor, which limits the application field of epoxy resin paint.

[0003] Adding an antistatic agent to the epoxy floor paint can effectively improve its anti-static effect. Common antistatic agents include conductive carbon black and graphene. However, the use of conductive carbon black in large quantities has a significant impact on the performance of the paint. Graphene is expensive and difficult to commercialize and practical application. Quaternary ammonium salt cationic antistatic agents have diverse preparation methods and good compatibility with high molecular materials, and have important applications in coatings, films, pipes, rubber and other aspects. SUMMARY

[0004] (I) The technical problem solved by the present application is to solve the problem of poor anti-static performance of epoxy floor paint.

[0005] (II) Technical scheme: A preparation method of an anti-static epoxy floor paint: (1) Add active diluent, epoxy resin, filler, dispersant, defoaming agent and leveling agent to a container, stir and mix uniformly to obtain an epoxy emulsion component.

[0006] (2) Add water, water-based epoxy curing agent and end-thiol cationic rosin polymer to a container, stir and mix uniformly to obtain a curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix uniformly to obtain the anti-static epoxy floor paint.

[0007] Preferably, the mass ratio of active diluent, epoxy resin, filler, dispersant, defoaming agent, leveling agent, water, water-based epoxy curing agent and end-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).

[0008] Preferably, the active diluent is butyl glycidyl ether, ethylene glycol diglycidyl ether or neopentyl glycol diglycidyl ether.

[0009] Preferably, the filler includes any one or combination of silicon powder, quartz powder, calcium carbonate, barium sulfate, and talc powder.

[0010] Preferably, the preparation method of the terminal mercapto cationic rosin polymer comprises the following steps: (1) adding toluene solvent, rosin acid, 2-chloroethanol, and p-toluenesulfonic acid in a molar ratio of 1:(1.4-2):(0.2-0.3) into a reaction container, heating to 80-100 DEG C, and reacting for 10-18 h, then distilling under reduced pressure, and recrystallizing the product in dichloromethane to obtain chloroacetate rosin.

[0011] (2) adding N,N-dimethylacetamide solvent, N-methylallylamine, dimercaptoethanol glycol, and triethylamine into a reaction container, stirring and reacting for 2-3 h at 15-25 DEG C, then adding chloroacetate rosin, wherein the molar ratio of N-methylallylamine, dimercaptoethanol glycol, triethylamine, and chloroacetate rosin is 1:(1.1-1.2):(0.012-0.016):(0.4-1.2), passing nitrogen, heating to 80-110 DEG C, stirring and reacting for 24-48 h, pouring the solution into ethanol, stirring, filtering, washing the precipitate with ethanol, and drying to obtain the terminal mercapto cationic rosin polymer.

[0012] (Three) beneficial technical effects: the terminal mercapto cationic rosin polymer is obtained by subjecting N-methylallylamine and dimercaptoethanol glycol to a mercapto-alkene polymerization reaction, and then to a quaternary ammonium reaction with chloroacetate rosin, and is blended with epoxy resin, water-based epoxy curing agent Yinchuang WH-1000, etc., to obtain anti-static epoxy resin floor coating.

[0013] The terminal mercapto cationic rosin polymer of the present application contains terminal mercapto groups, can react with epoxy groups of epoxy resin, thereby bonding the cationic rosin polymer to the curing system of the epoxy resin, and the rosin contains rigid and stable fused rings and has strong hydrophobicity, and introduction into the molecular chain of the epoxy resin can improve the pencil hardness, wear resistance, corrosion resistance, and water resistance of the floor coating.

[0014] The cationic rosin polymer of the present application contains quaternary ammonium salt antistatic groups, and introduction into the molecular chain of the epoxy resin can form a conductive layer on the surface of the coating film, accelerate charge dissipation, is beneficial to reducing surface resistance, and plays a good anti-static effect. DETAILED DESCRIPTION

[0015] Example 1 (1) Into a reaction vessel was added 0.8 L of toluene solvent, 0.3 mol of abietic acid, 0.42 mol of 2-chloroethanol, and 0.09 mol of p-toluenesulfonic acid, heated to 80°C, and reacted for 18 h. After distillation under reduced pressure, the product was recrystallized in dichloromethane to obtain a chloroacetate rosin. The preparation reaction formula is as follows: .

[0016] (2) Into a reaction vessel was added 1.2 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyl diallylamine, 0.55 mol of ethylene glycol dimercaptoacetate, and 7.2 mmol of triethylamine, stirred at 25°C for 2 h, then 0.35 mol of chloroacetate rosin was added, nitrogen was introduced, heated to 110°C, and stirred for 24 h. The solution was poured into ethanol, stirred, filtered, the precipitate was washed with ethanol, and dried to obtain a thiol-terminated cationic rosin polymer. The preparation reaction formula is as follows: .

[0017] (3) Into a container was added 200 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 460 g of silicon powder, 260 g of talc powder, 15 g of dispersant Dispex CX 4320AM, 10 g of defoaming agent Dow Corning AFE-1247, and 7 g of leveling agent Shengsheng SSL-311, and stirred to obtain an epoxy emulsion component.

[0018] (4) Into a container was added 180 g of water, 460 g of waterborne epoxy curing agent Yingchuang WH-1000, and 80 g of thiol-terminated cationic rosin polymer, and stirred to obtain a curing agent component. Then the curing agent component was added to the epoxy emulsion component, and stirred to obtain an antistatic epoxy resin floor coating.

[0019] Example 2 (1) Into a reaction vessel was added 1 L of toluene solvent, 0.3 mol of abietic acid, 0.6 mol of 2-chloroethanol, and 0.06 mol of p-toluenesulfonic acid, heated to 100°C, and reacted for 10 h. During the reaction, reflux condensation was carried out. After distillation under reduced pressure, the product was recrystallized in dichloromethane to obtain a chloroacetate rosin.

[0020] (2) Into a reaction vessel was added 1.5 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyl diallylamine, 0.6 mol of ethylene glycol dimercaptoacetate, and 8 mmol of triethylamine, stirred at 15°C for 3 h, then 0.2 mol of chloroacetate rosin was added, nitrogen was introduced, heated to 100°C, and stirred for 48 h. The solution was poured into ethanol, stirred, filtered, the precipitate was washed with ethanol, and dried to obtain a thiol-terminated cationic rosin polymer.

[0021] (3) Into a container, 120 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 490 g of silica powder, 270 g of barium sulfate, 12 g of dispersant Dispex CX 4320AM, 10 g of defoaming agent Dow Corning AFE-1247, and 7 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0022] (4) Into a container, 160 g of water, 420 g of water-based epoxy curing agent Wincrete WH-1000, and 120 g of mercaptoterminal cationic rosin polymer were added and stirred to obtain a curing agent component. Then, the curing agent component was added to the epoxy emulsion component and stirred to obtain an antistatic epoxy resin floor paint.

[0023] Example 3 (1) Into a reaction container, 1.5 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyldiallylamine, 0.58 mol of dimercaptoethyl glycolate, and 6 mmol of triethylamine were added and stirred at 25°C for 2 h. Then, 0.6 mol of chloroacetate rosin (prepared in Example 1) was added, nitrogen was introduced, and the solution was heated to 80°C and stirred for 48 h. The solution was poured into ethanol, stirred, and filtered. The precipitate was washed with ethanol and dried to obtain a mercaptoterminal cationic rosin polymer.

[0024] (2) Into a container, 200 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 570 g of quartz powder, 230 g of talc, 20 g of dispersant Dispex CX 4320AM, 9 g of defoaming agent Dow Corning AFE-1247, and 5 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0025] (3) Into a container, 140 g of water, 370 g of water-based epoxy curing agent Wincrete WH-1000, and 160 g of mercaptoterminal cationic rosin polymer were added and stirred to obtain a curing agent component. Then, the curing agent component was added to the epoxy emulsion component and stirred to obtain an antistatic epoxy resin floor paint.

[0026] Example 4 (1) Into a reaction container, 1.4 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyldiallylamine, 0.6 mol of dimercaptoethyl glycolate, and 6.4 mmol of triethylamine were added and stirred at 20°C for 3 h. Then, 0.5 mol of chloroacetate rosin (prepared in Example 1) was added, nitrogen was introduced, and the solution was heated to 100°C and stirred for 36 h. The solution was poured into ethanol, stirred, and filtered. The precipitate was washed with ethanol and dried to obtain a mercaptoterminal cationic rosin polymer.

[0027] (2) Into a container, 136 g of neopentyl glycol diglycidyl ether, 1 kg of epoxy resin E51, 430 g of silica powder, 220 g of calcium carbonate, 17 g of dispersant Dispex CX 4320AM, 6 g of defoaming agent Dow Corning AFE-1247, 8 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0028] (3) Into a container, 100 g of water, 320 g of waterborne epoxy curing agent Wincrete WH-1000, 200 g of mercaptoterminal cationic rosin polymer were added and stirred to obtain a curing agent component; then the curing agent component was added to the epoxy emulsion component and stirred to obtain an antistatic epoxy resin floor coating.

[0029] Comparative Example 1 (1) Into a container, 200 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 460 g of silica powder, 260 g of talc, 15 g of dispersant Dispex CX 4320AM, 10 g of defoaming agent Dow Corning AFE-1247, 7 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0030] (2) Into a container, 180 g of water, 460 g of waterborne epoxy curing agent Wincrete WH-1000 were added and stirred to obtain a curing agent component; then the curing agent component was added to the epoxy emulsion component and stirred to obtain an epoxy resin floor coating.

[0031] Comparative Example 2 (1) Into a reaction container, 1.2 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyldiallylamine, 0.55 mol of dimercaptoethyl glycol, 7.2 mmol of triethylamine were added and stirred at 25°C for 2 h, N,N-dimethylacetamide was removed by distillation under reduced pressure, washed with petroleum ether, and dried to obtain a mercaptoterminal polymer.

[0032] (2) Into a container, 200 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 460 g of silica powder, 260 g of talc, 15 g of dispersant Dispex CX 4320AM, 10 g of defoaming agent Dow Corning AFE-1247, 7 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0033] (3) Into a container, 180 g of water, 460 g of waterborne epoxy curing agent Wincrete WH-1000, 80 g of mercaptoterminal polymer were added and stirred to obtain a curing agent component; then the curing agent component was added to the epoxy emulsion component and stirred to obtain an epoxy resin floor coating.

[0034] Comparative Example 3 (1) Into a reaction vessel, 1.2 L of N,N-dimethylacetamide solvent, 0.5 mol of N-methyl diallylamine, 0.55 mol of ethylene glycol dimercaptoacetate, 7.2 mmol of triethylamine were added, and the reaction was stirred at 25°C for 2 h, then 0.35 mol of ethyl chloroacetate was added, nitrogen was introduced, and the reaction was stirred at 110°C for 24 h. The solution was poured into ethanol, stirred and filtered, and the precipitate was washed with ethanol and dried to obtain a terminal mercapto cationic polymer.

[0035] (2) Into a container, 200 g of butyl glycidyl ether, 1 kg of epoxy resin E51, 460 g of silicon powder, 260 g of talc powder, 15 g of dispersant Dispex CX 4320AM, 10 g of defoaming agent Dow Corning AFE-1247, and 7 g of leveling agent Shengsheng SSL-311 were added and stirred to obtain an epoxy emulsion component.

[0036] (3) Into a container, 180 g of water, 460 g of waterborne epoxy curing agent Wincrete WH-1000, and 80 g of terminal mercapto cationic polymer were added and stirred to obtain a curing agent component; then the curing agent component was added to the epoxy emulsion component and stirred to obtain an epoxy resin floor coating.

[0037] The performance of the floor coating film was tested according to the standard SJ / T 11294-2018. The results are shown in Table 1.

[0038] Table 1 Performance test of epoxy resin floor coating Group Point-to-point resistance (Ω) Pencil hardness Abrasion resistance (g) Corrosion resistance (20% NaOH solution, 144 h) Water resistance (360 h) Example 1 4.78 x 10 7 ]] 4H 0.033 No blister, no peeling No blister, no peeling Example 2 9.13 x 10 6 ]] 3H 0.037 No blister, no peeling No blister, no peeling Example 3 6.25 x 10 5 ]] 5H 0.018 No blister, no peeling No blister, no peeling Example 4 1.06 x 10 5 ]] 3H 0.026 Blisters, no peeling No blister, no peeling Comparative Example 1 8.31 x 10 11 ]] 3H 0.047 Blisters, peeling Blisters, no peeling Comparative Example 2 8.70 x 10 11 ]] 3H 0.044 Blisters, peeling No blister, no peeling Comparative Example 3 4.49 x 10 7 ]]> 3H 0.042 Blisters, peeling Blisters, peeling Compared with Comparative Examples 1-3, the epoxy resin floor coating of Example 1-4 added a terminal mercapto cationic rosin polymer, which contains a terminal mercapto group that can react with the epoxy group of the epoxy resin, thereby bonding the cationic rosin polymer to the curing system of the epoxy resin. The rosin contains a rigid and stable fused ring combination and is highly hydrophobic. When introduced into the molecular chain of the epoxy resin, it can improve the pencil hardness, wear resistance, corrosion resistance, and water resistance of the floor coating. At the same time, the cationic rosin polymer contains a quaternary ammonium salt antistatic group, which can form a conductive layer on the surface of the coating film, accelerate the dissipation of electric charge, and help to reduce the surface resistance, thereby playing a good antistatic effect.

Claims

1. A method for preparing an antistatic epoxy resin floor coating, characterized in that: The preparation method comprises the following steps: (1) Add active diluent, epoxy resin, filler, dispersant, defoamer, and leveling agent into a container, stir and mix to obtain epoxy emulsion component; (2) Add water, a water-based epoxy curing agent, and a terminal mercapto cationic rosin polymer into a container, stir and mix them evenly to obtain a curing agent component; then add the curing agent component to the epoxy emulsion component, stir and mix them evenly to obtain an antistatic epoxy resin floor coating.

2. The preparation method of the antistatic epoxy resin floor coating according to claim 1, characterized in that, The mass ratio of the active diluent, epoxy resin, filler, dispersant, defoamer, leveling agent, water, water-based epoxy curing agent, and terminal mercapto 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 preparation method of the 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 preparation method of the antistatic epoxy resin floor coating according to claim 2, characterized in that, The filler includes any one or a combination of silicon micropowder, quartz powder, calcium carbonate, barium sulfate, and talc powder.

5. The preparation method of the antistatic epoxy resin floor coating according to claim 2, characterized in that, Preparation method of the mercapto-terminated cationic rosin polymer: (1) Adding toluene solvent, rosin acid, 2-chloroethanol, and p-toluenesulfonic acid into a reaction vessel, performing vacuum distillation after the reaction, and recrystallizing the product to obtain chloroacetate rosin; (2) Add N,N-dimethylacetamide solvent, N-methyldiallylamine, ethylene glycol dimercaptoacetate, and triethylamine to a reaction vessel, stir and react at 15-25°C for 2-3 hours, then add chloroacetate rosin, introduce nitrogen, heat to 80-110°C, stir and react for 24-48 hours, pour the solution into ethanol, stir and filter, wash the precipitate, and dry to obtain a terminal mercapto cationic rosin polymer.

6. The method for preparing the antistatic epoxy resin floor coating according to claim 5, wherein: The molar ratio of rosin acid, 2-chloroethanol and p-toluenesulfonic acid in (1) is 1: (1.4-2): (0.2-0.3).

7. The method for preparing the antistatic epoxy resin floor coating according to claim 5, wherein: The reaction temperature in (1) is 80-100°C, and the reaction time is 10-18 hours.

8. The method for preparing the antistatic epoxy resin floor coating according to claim 5, wherein: The molar ratio of N-methyldiallylamine, ethylene glycol dimercaptoacetate, triethylamine and chloroacetate rosin in (2) is 1: (1.1-1.2): (0.012-0.016): (0.4-1.2).

9. An antistatic epoxy resin floor coating obtained by the preparation method according to any one of claims 1 to 8.