Impact-resistant industrial coating and manufacturing method thereof

Abstract

The invention discloses an impact-resistant industrial coating and a manufacturing method thereof, and relates to the technical field of industrial coatings. The impact-resistant industrial coating comprises the following raw materials in parts by weight: 80-100 parts of epoxy resin, 2-5 parts of graphene oxide, 3-5 parts of an antistatic agent, 5-8 parts of a modified thickener, 1-3 parts of a dispersant, 0.5-1.5 parts of a leveling agent, 2-3 parts of an antioxidant, 8-12 parts of a curing agent and 100-140 parts of deionized water. The preparation method comprises the following steps: reacting polyethylene glycol diethylene oxide methyl ether with 2-(methacrylic acid) ethyl ester 3, 5-diaminobenzoic acid to generate a polymer; reacting the polymer with 3-(dimethylamino)-1-propanethiol to generate a tertiary amine-terminated polymer; and carrying out quaternization reaction on the tertiary amine-terminated polymer and bromododecane to obtain the antistatic agent. The impact-resistant industrial coating prepared by the invention has excellent antistatic property and rheological property.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial coatings, and particularly relates to an impact-resistant industrial coating and a manufacturing method thereof. Background Art

[0002] In the modern industrial field, with the rapid development of manufacturing and the continuous improvement of material performance requirements, industrial coatings, as important materials for protecting and decorating various industrial products, directly affect the service life and quality stability of products. Impact-resistant industrial coatings, as a key protective material, have received extensive attention in recent years.

[0003] With the rapid development of high-precision and high-sensitivity industries such as electronics, electrical appliances, aviation, and chemical engineering, more stringent requirements are put forward for the impact resistance of industrial coatings. In practical applications, the generation of static electricity on the coating surface can cause various problems, such as interfering with production, causing sparks leading to explosions, and damaging the integrated circuits of electronic devices. The general method to remove static electricity is to use antistatic agents to reduce the surface resistance of polymers. Antistatic agents are a class of chemical additives that can prevent the generation of static charges or effectively dissipate static charges. They form leakage charge channels through the ion conduction or hygroscopic action of ionized groups or polar groups to achieve the purpose of antistatic. Commonly used antistatic agents include quaternary ammonium salts, alkyl phosphate esters, etc. In the field of industrial coatings, the optimization of rheological properties is also crucial for improving the comprehensive performance of coatings. Rheological properties not only affect the storage stability, construction performance, and quality of the final coating of coatings, but also directly relate to the applicability of coatings under different environmental conditions. However, there are still some problems in improving the rheological properties of industrial coatings. Therefore, it has become an urgent task to develop an industrial coating with excellent rheological properties and antistatic properties.

[0004] Chinese Patent No. CN118956221A discloses a weather-resistant industrial coating and a preparation method thereof. In this patent, a hexenyl ultraviolet absorber is prepared by reacting 6-chloro-1-hexene with 2,3-bis(2,4,5-trimethyl-3-thienyl) maleimide; a modified epoxy resin emulsion is prepared by reacting the hexenyl ultraviolet absorber, methacrylic acid with bisphenol A epoxy resin E51; a modified glass flake is prepared by polymerizing and growing 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dioxide and methylphenylsilanediol on a pre-modified glass flake; the modified epoxy resin emulsion, the modified glass flake, a self-healing curing agent, and an antifoaming agent are mixed evenly to prepare a weather-resistant industrial coating. This industrial coating has excellent anti-aging performance, but its antistatic performance is poor. Summary of the Invention

[0005] In view of the deficiencies in the existing technology, the purpose of the present invention is to provide an impact-resistant industrial coating and its manufacturing method.

[0006] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0007] An impact-resistant industrial coating, comprising raw materials in the following parts by weight:

[0008] 80 - 100 parts of epoxy resin, 2 - 5 parts of graphene oxide, 3 - 5 parts of antistatic agent, 5 - 8 parts of modified thickener, 1 - 3 parts of dispersant, 0.5 - 1.5 parts of leveling agent, 2 - 3 parts of antioxidant, 8 - 12 parts of curing agent, 100 - 140 parts of deionized water;

[0009] The antistatic agent is prepared by the following method:

[0010] S1: Polyethylene glycol bis(2 - methoxyethyl) ether, 2-(methacryloyloxy)ethyl 3,5 - diamino benzoate react under the catalysis of glacial acetic acid to form a polymer;

[0011] S2: Under nitrogen protection, the polymer reacts with 3-(dimethylamino)-1 - propanethiol under the action of initiator AIBN to form a terminal tertiary amine polymer;

[0012] S3: The terminal tertiary amine polymer reacts with dodecyl bromide to obtain the antistatic agent.

[0013] In step S1, the molar ratio of polyethylene glycol bis(2 - methoxyethyl) ether, 2-(methacryloyloxy)ethyl 3,5 - diamino benzoate is 1:(1 - 1.5).

[0014] In step S2, the mass ratio of the polymer, 3-(dimethylamino)-1 - propanethiol is (8 - 15):2.

[0015] In step S3, the mass ratio of the terminal tertiary amine polymer, dodecyl bromide is (3 - 5):1.

[0016] The modified thickener is prepared by the following method:

[0017] S1: Glyceric acid reacts with glycerol under the catalysis of p - toluenesulfonic acid to form hyperbranched polyester;

[0018] S2: Under nitrogen protection, toluene - 2,6 - diisocyanate, PEG800 react under the catalysis of dibutyltin dilaurate to obtain a polyurethane prepolymer; then octadecylamine polyoxyethylene ether is added for chain extension reaction to obtain long - chain grafted polyurethane;

[0019] S3: Under nitrogen protection, the long - chain grafted polyurethane reacts with hyperbranched polyester to obtain the modified thickener.

[0020] In step S1, the molar ratio of glyceric acid to glycerol in the feed is (9 - 12):1.

[0021] In step S2, the mass ratio of toluene 2,6 - diisocyanate, PEG800, and octadecylamine polyoxyethylene ether in the feed is 1:(3 - 5):(2 - 3).

[0022] In step S3, the mass ratio of the long - chain branched polyurethane to the hyperbranched polyester in the feed is (5 - 10):1.

[0023] The leveling agent is one of polyether - modified polysiloxane and polyester - modified polysiloxane; the dispersant is one of sodium dodecyl sulfate and sodium dodecylbenzenesulfonate; the antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 168; the curing agent is one of phthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0024] A method for manufacturing an impact - resistant industrial coating, comprising the following steps:

[0025] (1) Weigh by weight: 80 - 100 parts of epoxy resin, 2 - 5 parts of graphene oxide, 3 - 5 parts of antistatic agent, 5 - 8 parts of modified thickener, 1 - 3 parts of dispersant, 0.5 - 1.5 parts of leveling agent, 2 - 3 parts of antioxidant, 8 - 12 parts of curing agent, and 100 - 140 parts of deionized water;

[0026] (2) Add deionized water, epoxy resin, graphene oxide, dispersant, and antioxidant to a stirrer in sequence and stir for 10 - 30 min; then add the leveling agent, curing agent, and modified thickener, stir for 10 - 30 min, and finally add the antistatic agent and stir to mix evenly to obtain the impact - resistant industrial coating.

[0027] Due to the above - mentioned technical solutions, the beneficial effects of the present invention include:

[0028] (1) In the present invention, the epoxy group in polyethylene glycol diepoxyethyl methyl ether reacts with the amino group in 2 - (methacryloyl) ethyl 3,5 - diaminobenzoate to form a polymer; the double bond in the polymer reacts with the mercapto group in 3 - (dimethylamino) - 1 - propanethiol through a thiol - ene click reaction to form a terminal tertiary amine polymer; the terminal tertiary amine polymer undergoes a quaternization reaction with dodecyl bromide to obtain the antistatic agent.

[0029] (2) In the antistatic agent 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate prepared by the present invention, the amino groups react with epoxy groups to form a three-dimensional network structure, enhancing the solvent resistance and thermal stability; the terminal tertiary amine polymer undergoes quaternization reaction with dodecyl bromide to form a cationic quaternary ammonium salt, which neutralizes static charges through an ionic conduction mechanism; the long-chain dodecyl group enhances the hydrophobicity, enabling the quaternary ammonium salt to easily migrate to the coating surface for enrichment, improving the antistatic persistence; 3-(dimethylamino)-1-propanethiol introduces a thioether bond, relieving the internal stress in the coating, antioxidizing and hydrolytic resistance, and prolonging the antistatic life.

[0030] (3) In the present invention, hyperbranched polyester is generated by the reaction of the carboxyl group in glyceric acid with the hydroxyl group in glycerol under the catalysis of p-toluenesulfonic acid; toluene 2,6-diisocyanate and PEG800 react under the catalysis of dibutyltin dilaurate to obtain a polyurethane prepolymer, and then octadecylamine polyoxyethylene ether is added for chain extension reaction to obtain a long-chain grafted polyurethane; the isocyanate group in the long-chain grafted polyurethane reacts with the hydroxyl group in the hyperbranched polyester to obtain a modified thickener.

[0031] (4) The modified thickener prepared by the present invention has a hyperbranched structure, which enables less entanglement between molecules in the solution, having good fluidity and low viscosity characteristics. At low shear rates, it can thicken rapidly, while at high shear rates, its viscosity decreases rapidly, showing good shear thinning behavior. This rheological property makes the system containing the modified thickener operate more smoothly during construction, not prone to sagging, and can maintain a good consistency during standing, preventing precipitation of solid components such as pigments. Detailed implementation mode

[0032] The following is further illustrated with reference to examples, but the present invention is not limited to these examples.

[0033] Example 1 Preparation of antistatic agent:

[0034] S1: Add 200 ml of DMF, 0.1 mol of polyethylene glycol bis(2-oxiranylmethyl) ether, and 0.1 mol of 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate to a reactor, stir and mix evenly, heat up to 80 °C, then add 6 g of glacial acetic acid, react for 6 h, cool to room temperature, add 50 ml of deionized water for dilution, carry out vacuum distillation at 80 °C for 4 h, add 100 ml of saturated sodium chloride solution, stir and let stand for 10 minutes, extract with dichloromethane (150 ml × 3 times), combine the organic phases, add 50 g of anhydrous sodium sulfate, stir and dry for 2 h, and concentrate under reduced pressure at 40 °C for 2 h; drop the concentrated solution into 300 ml of ice-cold ether drop by drop while stirring to precipitate the polymer, filter with a Buchner funnel and wash with ether three times (40 ml each time), and finally dry in vacuo at 40 °C for 24 hours to obtain the polymer;

[0035] S2: Under nitrogen protection, add 1200 ml of DMSO, 40 g of 3-(dimethylamino)-1-propanethiol, and 160 g of the polymer into the reactor, stir, then add 5 g of initiator AIBN, heat up to 60 °C, react for 12 h, then perform vacuum distillation at 70 °C for 5 h. Drop the concentrated solution into 500 ml of ice-cold ether and stir to precipitate the polymer. Filter it through a Buchner funnel and wash it three times with ether (80 ml each time). Dry it in vacuum at 50 °C for 24 h to obtain the terminal tertiary amine polymer;

[0036] S3: Add 1000 ml of toluene and 90 g of the terminal tertiary amine polymer into the reactor, stir and mix evenly, then slowly dropwise add 30 g of dodecyl bromide over 10 min. After dropping, reflux and react for 5 h, then perform vacuum distillation at 65 °C for 4 h. Recrystallize it three times with an acetone / ethanol mixed solution (acetone / ethanol (V / V) = 9:1) (300 ml of the mixed solution each time). Dry it in vacuum at 60 °C for 5 h to obtain the antistatic agent.

[0037] Example 2 Preparation of the antistatic agent:

[0038] S1: Add 200 ml of DMF, 0.1 mol of polyethylene glycol diglycidyl methyl ether, and 0.12 mol of 2-(methacryloyl)ethyl 3,5-diaminobenzoate into the reactor, stir and mix evenly, heat up to 90 °C, then add 7 g of glacial acetic acid. After reacting for 5 h, cool to room temperature, add 50 ml of deionized water for dilution, perform vacuum distillation at 80 °C for 4 h, add 100 ml of saturated sodium chloride solution, stir and let it stand for 10 minutes, extract with dichloromethane (150 ml × 3 times), combine the organic phases, add 50 g of anhydrous sodium sulfate, stir and dry for 2 h, and concentrate under reduced pressure at 40 °C for 2 h; Drop the concentrated solution into 300 ml of ice-cold ether and stir to precipitate the polymer. Filter it through a Buchner funnel and wash it three times with ether (40 ml each time). Finally, dry it in vacuum at 40 °C for 24 hours to obtain the polymer;

[0039] S2: Under nitrogen protection, add 1500 ml of DMSO, 40 g of 3-(dimethylamino)-1-propanethiol, and 240 g of the polymer into the reactor, stir, then add 5 g of initiator AIBN, heat up to 70 °C, react for 10 h, then perform vacuum distillation at 70 °C for 5.5 h. Drop the concentrated solution into 700 ml of ice-cold ether and stir to precipitate the polymer. Filter it through a Buchner funnel and wash it three times with ether (80 ml each time). Dry it in vacuum at 50 °C for 24 h to obtain the terminal tertiary amine polymer;

[0040] S3: Add 1000 ml of toluene and 120 g of terminal tertiary amine polymer into the reactor, stir to mix evenly, then slowly dropwise add 30 g of dodecyl bromide over 10 min. After the dropping is completed, reflux for 6 h, then perform vacuum distillation at 50 °C for 3 h. Recrystallize three times with an acetone / ethanol mixed solution (acetone / ethanol (V / V) = 9:1) (using 400 ml of the mixed solution each time), and dry in vacuum at 70 °C for 4 h to obtain the antistatic agent.

[0041] Preparation of the antistatic agent in Example 3:

[0042] S1: Add 200 ml of DMF, 0.1 mol of polyethylene glycol bis(2-methoxyethyl) ether, and 0.15 mol of 3,5-diaminobenzoic acid 2-(methacryloyloxy)ethyl ester into the reactor, stir to mix evenly, heat up to 100 °C, then add 8 g of glacial acetic acid. After reacting for 4 h, cool to room temperature, add 50 ml of deionized water for dilution, perform vacuum distillation at 80 °C for 4 h, add 100 ml of saturated sodium chloride solution, stir and let stand for 10 minutes, extract with dichloromethane (150 ml × 3 times), combine the organic phases, add 50 g of anhydrous sodium sulfate, stir and dry for 2 h, and concentrate under reduced pressure at 40 °C for 2 h; drop the concentrated solution dropwise into 300 ml of ice-cold diethyl ether while stirring to precipitate the polymer, filter with a Buchner funnel and wash three times with diethyl ether (40 ml each time), and finally dry in vacuum at 40 °C for 24 h to obtain the polymer;

[0043] S2: Under nitrogen protection, add 1600 ml of DMSO, 40 g of 3-(dimethylamino)-1-propanethiol, and 300 g of the polymer into the reactor, stir, then add 5 g of initiator AIBN, heat up to 80 °C, react for 8 h, then perform vacuum distillation at 70 °C for 6 h, drop the concentrated solution into 700 ml of ice-cold diethyl ether while stirring to precipitate the polymer, filter with a Buchner funnel and wash three times with diethyl ether (80 ml each time), and dry in vacuum at 50 °C for 24 h to obtain the terminal tertiary amine polymer;

[0044] S3: Add 1000 ml of toluene and 150 g of terminal tertiary amine polymer into the reactor, stir to mix evenly, then slowly dropwise add 30 g of dodecyl bromide over 10 min. After the dropping is completed, reflux for 7 h, then perform vacuum distillation at 60 °C for 2 h. Recrystallize three times with an acetone / ethanol mixed solution (acetone / ethanol (V / V) = 9:1) (using 400 ml of the mixed solution each time), and dry in vacuum at 80 °C for 3 h to obtain the antistatic agent.

[0045] Preparation of the modified thickener in Example 4:

[0046] S1: Under nitrogen protection, add 400 ml of toluene, 0.9 mol of glyceric acid, and 0.1 mol of glycerol into the reactor, stir and mix evenly, then add 8 g of p-toluenesulfonic acid, heat up to reflux and react for 6 h (remove the generated water using a water separator during the reaction), then cool to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral (neutral in this application means pH = 7), stir well for 30 min, let it stand for layering, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain hyperbranched polyester;

[0047] S2: Under nitrogen protection, add 500 ml of DMF and 10 g of toluene 2,6-diisocyanate into the reactor, stir to dissolve, heat up to 50 °C, then slowly dropwise add 30 g of PEG800 over 20 min. After dropping, add 3 g of dibutyltin dilaurate and react for 6 h to obtain a polyurethane prepolymer; then add 20 g of octadecylamine polyoxyethylene ether, continue to react for 4 h, then add 800 ml of ice water for precipitation and filtration, and dry in vacuum at 50 °C for 6 h to obtain long-chain grafted polyurethane;

[0048] S3: Under nitrogen protection, add 600 ml of DMF, 50 g of long-chain grafted polyurethane, and 10 g of hyperbranched polyester into the reactor, stir and mix evenly, heat up to 70 °C, then add 5 g of dibutyltin dilaurate, react for 4 h, distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain a modified thickener.

[0049] Preparation of the modified thickener in Example 5:

[0050] S1: Under nitrogen protection, add 500 ml of toluene, 1.0 mol of glyceric acid, and 0.1 mol of glycerol into the reactor, stir and mix evenly, then add 8 g of p-toluenesulfonic acid, heat up to reflux and react for 8 h (remove the generated water using a water separator during the reaction), then cool to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral, stir well for 30 min, let it stand for layering, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain hyperbranched polyester;

[0051] S2: Under nitrogen protection, add 500 ml of DMF and 10 g of toluene 2,6-diisocyanate into the reactor, stir to dissolve, heat up to 60 °C, then slowly dropwise add 40 g of PEG800 over 20 min. After dropping, add 3 g of dibutyltin dilaurate and react for 5 h to obtain a polyurethane prepolymer; then add 25 g of octadecylamine polyoxyethylene ether, continue to react for 5 h, then cool to room temperature, add 800 ml of ice water for precipitation and filtration, and dry in vacuum at 50 °C for 6 h to obtain long-chain grafted polyurethane;

[0052] S3: Under nitrogen protection, add 600 ml of DMF, 80 g of long-chain grafted polyurethane, and 10 g of hyperbranched polyester into the reactor, stir to mix evenly, heat up to 80 °C, then add 5 g of dibutyltin dilaurate, react for 3 h, then distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain the modified thickener.

[0053] Preparation of the modified thickener in Example 6:

[0054] S1: Under nitrogen protection, add 600 ml of toluene, 1.2 mol of glyceric acid, and 0.1 mol of glycerol into the reactor, stir to mix evenly, then add 8 g of p-toluenesulfonic acid, heat up to reflux and react for 10 h (remove the generated water using a water separator during the reaction), then cool to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral, stir well for 30 min, let it stand for layering, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain hyperbranched polyester;

[0055] S2: Under nitrogen protection, add 500 ml of DMF and 10 g of toluene 2,6-diisocyanate into the reactor, stir to dissolve, heat up to 70 °C, then slowly dropwise add 50 g of PEG800 over 20 min. After dropping, add 4 g of dibutyltin dilaurate, react for 4 h to obtain a polyurethane prepolymer; then add 30 g of octadecylamine polyoxyethylene ether, continue to react for 6 h, then cool to room temperature, add 800 ml of ice water for precipitation and filtration, and dry in vacuum at 50 °C for 6 h to obtain long-chain grafted polyurethane;

[0056] S3: Under nitrogen protection, add 600 ml of DMF, 100 g of long-chain grafted polyurethane, and 10 g of hyperbranched polyester into the reactor, stir to mix evenly, heat up to 90 °C, then add 5 g of dibutyltin dilaurate, react for 2 h, then distill under reduced pressure at 70 °C for 4 h, and dry in vacuum at 70 °C for 5 h to obtain the modified thickener.

[0057] Preparation of the impact-resistant industrial coating in Example 7:

[0058] (1) Weigh: 800 g of epoxy resin, 20 g of graphene oxide, 30 g of antistatic agent (prepared in Example 1), 50 g of modified thickener (prepared in Example 4), 10 g of dispersant (sodium dodecyl sulfate), 5 g of leveling agent (polyether-modified polysiloxane), 20 g of antioxidant (antioxidant 1010), 80 g of curing agent (phthalic anhydride), 1000 g of deionized water;

[0059] (2) Add deionized water, epoxy resin, graphene oxide, dispersant, and antioxidant to the stirrer in sequence and stir for 10 min; then add the leveling agent, curing agent, and modified thickener, stir for 10 min, and finally add the antistatic agent and stir to mix evenly to obtain the impact-resistant industrial coating.

[0060] Example 8 Preparation of Impact-Resistant Industrial Coating:

[0061] (1) Weigh: 900 g of epoxy resin, 35 g of graphene oxide, 40 g of antistatic agent (prepared in Example 2), 65 g of modified thickener (prepared in Example 5), 20 g of dispersant (sodium dodecylbenzenesulfonate), 10 g of leveling agent (polyester-modified polysiloxane), 25 g of antioxidant (antioxidant 1076), 100 g of curing agent (hexahydrophthalic anhydride), and 1200 g of deionized water;

[0062] (2) Add deionized water, epoxy resin, graphene oxide, dispersant, and antioxidant to the stirrer in sequence and stir for 20 min; then add the leveling agent, curing agent, and modified thickener, stir for 20 min, and finally add the antistatic agent and stir evenly to obtain the impact-resistant industrial coating.

[0063] Example 9 Preparation of Impact-Resistant Industrial Coating

[0064] (1) Weigh: 1000 g of epoxy resin, 50 g of graphene oxide, 50 g of antistatic agent (prepared in Example 3), 80 g of modified thickener (prepared in Example 6), 30 g of dispersant (sodium dodecylbenzenesulfonate), 15 g of leveling agent (polyether-modified polysiloxane), 30 g of antioxidant (antioxidant 168), 120 g of curing agent (methyltetrahydrophthalic anhydride), and 1400 g of deionized water;

[0065] (2) Add deionized water, epoxy resin, graphene oxide, dispersant, and antioxidant to the stirrer in sequence and stir for 30 min; then add the leveling agent, curing agent, and modified thickener, stir for 30 min, and finally add the antistatic agent and stir evenly to obtain the impact-resistant industrial coating.

[0066] Comparative Example 1

[0067] A method for manufacturing an impact-resistant industrial coating is basically the same as that in Example 8, except that the antistatic agent is replaced with an antistatic agent of equal weight prepared by the following method:

[0068] The preparation method of the antistatic agent is basically the same as that in Example 2, except that 2-(methacryloyl)ethyl 3,5-diaminobenzoate in step S1 is replaced with 2-aminostyrene of equal weight.

[0069] Comparative Example 2

[0070] A method for manufacturing an impact-resistant industrial coating is basically the same as that in Example 8, except that the antistatic agent is replaced with an antistatic agent of equal weight prepared by the following method:

[0071] The preparation method of the antistatic agent is basically the same as that of Example 2, except that the polyethylene glycol bis(2-methoxyethyl) ether in step S1 is replaced with diglycidyl ether of the same weight.

[0072] Comparative Example 3

[0073] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the antistatic agent is replaced with an antistatic agent of the same weight prepared by the following method:

[0074] The preparation method of the antistatic agent is basically the same as that of Example 2, except that 3-(dimethylamino)-1-propanethiol in step S2 is replaced with 3-dimethylamino-1-propanol of the same weight.

[0075] Comparative Example 4

[0076] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the antistatic agent is replaced with an antistatic agent of the same weight prepared by the following method:

[0077] The preparation method of the antistatic agent is basically the same as that of Example 2, except that dodecyl bromide in step S3 is replaced with bromobutane of the same weight.

[0078] Comparative Example 5

[0079] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the modified thickener is replaced with a modified thickener of the same weight prepared by the following method:

[0080] The preparation method of the modified thickener is basically the same as that of Example 5, except that glyceric acid in step S1 is replaced with 3-hydroxypropionic acid of the same weight.

[0081] Comparative Example 6

[0082] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the modified thickener is replaced with a modified thickener of the same weight prepared by the following method:

[0083] The preparation method of the modified thickener is basically the same as that of Example 5, except that glycerol in step S1 is replaced with pentaerythritol of the same weight.

[0084] Comparative Example 7

[0085] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the modified thickener is replaced with a modified thickener of the same weight prepared by the following method:

[0086] The preparation method of the modified thickener is basically the same as that of Example 5, except that the octadecylamine polyoxyethylene ether in step S2 is replaced with an equal weight of dodecylamine polyoxyethylene (5) ether.

[0087] Comparative Example 8

[0088] The manufacturing method of an impact-resistant industrial coating is basically the same as that of Example 8, except that the modified thickener is replaced with an equal weight of a modified thickener prepared by the following method:

[0089] S1: Under nitrogen protection, add 500 ml of toluene, 1.0 mol of glyceric acid, and 0.1 mol of glycerol to the reactor, stir and mix evenly, then add 8 g of p-toluenesulfonic acid, heat up to reflux and react for 8 h (remove the generated water using a water separator during the reaction), then cool to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral, stir well for 30 min, let it stand for stratification, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry in vacuum at 70 °C for 5 h to obtain hyperbranched polyester;

[0090] S2: Under nitrogen protection, add 1000 ml of DMF and 10 g of toluene 2,6-diisocyanate to the reactor, stir to dissolve, heat up to 60 °C, then slowly dropwise add 40 g of PEG800 over 20 min. After dropping, add 3 g of dibutyltin dilaurate and react for 5 h to obtain a polyurethane prepolymer;

[0091] Under nitrogen protection, add 500 ml of DMF and 10 g of toluene 2,6-diisocyanate to the reactor, stir to dissolve, heat up to 60 °C, then slowly dropwise add 40 g of PEG800 over 20 min. After dropping, add 3 g of dibutyltin dilaurate and react for 5 h. Cool to room temperature, add 800 ml of ice water for precipitation and filtration, and dry in vacuum at 50 °C for 6 h to obtain a polyurethane prepolymer;

[0092] S3: Under nitrogen protection, add 600 ml of DMF, 80 g of polyurethane prepolymer, and 10 g of hyperbranched polyester to the reactor, stir and mix evenly, heat up to 80 °C, then add 5 g of dibutyltin dilaurate and react for 3 h. Then distill under reduced pressure at 70 °C for 3 h and dry in vacuum at 70 °C for 5 h to obtain the modified thickener.

[0093] Comparative Example 9

[0094] A weather-resistant industrial coating prepared using the raw material composition, ratio, and method of Example 2 of the Chinese invention patent with the publication number CN118956221A.

[0095] In the examples and comparative examples of this application, the epoxy resin model used is E-51; the thickness of graphene oxide is 0.8 - 1.2 nm, and the sheet diameter is 1 - 5 μm, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; the polyether-modified polysiloxane model is BYK-333; the polyester-modified polysiloxane model is BYK-310.

[0096] Perform performance tests on the impact-resistant industrial coatings prepared in Examples 7 - 9 and Comparative Examples 1 - 9 of this application, and the test results are shown in Table 1.

[0097] According to GB / T 33328-2016, use a ZC36 type high resistance meter to test the surface resistivity of the industrial coating in a specific environment (temperature is 23°C, relative humidity is 50%), and set the test voltage to 500V DC.

[0098] Use a rotational viscometer to test the thixotropic index of the industrial coating: According to GB / T2794-2022, use an NDJ-4 type rotational viscometer, select 2 gear speeds (6r / min and 60r / min), and test the viscosity thixotropic index TI = η6 / η60 of the sample at room temperature.

[0099] Table 1 Performance Test Table

[0100] Project Surface resistivity Ω Thixotropic index Example 7 <![CDATA[3.2×10 7 > 3.5 Example 8 <![CDATA[2.8×10 7 > 3.8 Example 9 <![CDATA[3.5×10 7 > 3.6 Comparative Example 1 <![CDATA[4.8×10 9 > / Comparative Example 2 <![CDATA[6.4×10 8 > / Comparative Example 3 <![CDATA[2.7×10 8 > / Comparative Example 4 <![CDATA[7.3×10 8 > / Comparative Example 5 <![CDATA[3.6×10 7 > 1.6 Comparative Example 6 <![CDATA[3.4×10 7 > 1.8 Comparative Example 7 <![CDATA[3.1×10 7 > 2.0 Comparative Example 8 <![CDATA[3.3×10 7 > 2.4 Comparative Example 9 <![CDATA[4.3×10 8 > 2.7

[0101] It can be seen from Table 1 that the industrial coatings prepared in this application have good antistatic performance and rheological properties.

[0102] Comparative Example 1 is a comparative example in which 2-(methacryloyl)ethyl 3,5-diaminobenzoate in Step S1 of the antistatic agent preparation process is replaced by 2-vinyl aniline; Comparative Example 2 is a comparative example in which polyethylene glycol diglycidyl methyl ether in Step S1 of the antistatic agent preparation process is replaced by diglycidyl ether; Comparative Example 3 is a comparative example in which 3-(dimethylamino)-1-propanethiol in Step S2 of the antistatic agent preparation process is replaced by 3-dimethylamino-1-propanol; Comparative Example 4 is a comparative example in which 1-bromododecane in Step S3 of the antistatic agent preparation process is replaced by 1-bromobutane; As can be seen from Table 1, the antistatic effects are all inferior to those of the present application. This is because the polyethylene glycol segment in the main chain endows the polymer with excellent flexibility and hydrophilicity. During the film-forming process of the coating, the flexible segment helps the antistatic agent to be evenly dispersed in the coating, avoiding phase separation caused by excessive rigidity. The amino group in 2-(methacryloyl)ethyl 3,5-diaminobenzoate reacts with the epoxy group in polyethylene glycol diglycidyl methyl ether to form a three-dimensional network structure, improving the solvent resistance and thermal stability of the antistatic agent and avoiding performance degradation caused by high temperature or solvent erosion. The terminal tertiary amine polymer undergoes a quaternization reaction with 1-bromododecane to form a cationic quaternary ammonium salt, and its cation can adsorb anions in the environment to form an electric double layer, quickly neutralizing static charges through the ion conduction mechanism. The introduction of the long-chain dodecyl group enhances the hydrophobicity, making the quaternary ammonium salt more likely to migrate to the surface of the coating and accumulate, improving the antistatic persistence. The introduction of 3-(dimethylamino)-1-propanethiol introduces a thioether bond. The flexibility and chemical stability of the thioether bond can relieve the internal stress during the curing of the coating, avoiding the failure of the antistatic agent due to brittle fracture. At the same time, the thioether bond has antioxidant and hydrolysis resistance, which can slow down the decomposition of the quaternary ammonium salt in a humid environment and extend the antistatic life.

[0103] Comparative Example 5 is a comparative example in which glyceric acid in Step S1 during the preparation of the modified thickener is replaced by 3-hydroxypropionic acid. Comparative Example 6 is a comparative example in which glycerol in Step S1 during the preparation of the modified thickener is replaced by pentaerythritol. Comparative Example 7 is a comparative example in which octadecylamine polyoxyethylene ether in Step S2 during the preparation of the modified thickener is replaced by dodecylamine polyoxyethylene (5) ether. Comparative Example 8 is a comparative example in which octadecylamine polyoxyethylene ether is not added during the preparation of the modified thickener. As can be seen from Table 1, this is because the hyperbranched polyester formed by the polycondensation of glyceric acid and glycerol has a three-dimensional dendritic structure containing a large number of terminal hydroxyl groups, forming a dense intermolecular hydrogen bond network. This high-density polar group significantly improves the structural viscosity of the system and endows the coating with excellent thixotropic recovery. Compared with linear thickeners, the rigid backbone of the hyperbranched core can maintain part of the network structure under shear force, reducing viscosity collapse at high shear rates. The polyurethane prepolymer formed by PEG800 and toluene diisocyanate introduces octadecyl hydrophobic long chains through chain extension, which form physical micelles through hydrophobic association in the coating, further strengthening the network structure. The micelles exist stably under static conditions and dissociate under shear action, achieving significant thixotropy and effectively balancing storage stability. The hydroxyl groups of the hyperbranched polyester form reversible hydrogen bonds with the carbamate groups (-NHCOO-) in the polyurethane. This dynamic network dissociates partially during construction shear and reorganizes rapidly at rest, achieving the balance of shear thinning and thixotropy. The terminal hydroxyl groups of the hyperbranched polyester react with the isocyanate groups (-NCO) of the polyurethane to form stable carbamate bonds (-NHCOO-), constructing a hyperbranched-linear hybrid network. This chemical bonding avoids the separation of the two-phase interface, enhances the compatibility between the thickener and the resin matrix, and reduces viscosity fluctuations caused by phase separation during storage.

[0104] Comparative Example 9 is a weather-resistant industrial coating prepared by using the raw material composition, ratio, and method of Example 2 of the Chinese invention patent with the publication number CN118956221A, and its antistatic property and rheological properties are inferior to those of the present application.

[0105] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. However, for those of ordinary skill in the art, within the scope of the technical solution of the present invention, any equivalent changes such as slight modifications, evolutions, and variations made using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. An impact-resistant industrial coating, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of epoxy resin, 2-5 parts of graphene oxide, 3-5 parts of antistatic agent, 5-8 parts of modified thickener, 1-3 parts of dispersant, 0.5-1.5 parts of leveling agent, 2-3 parts of antioxidant, 8-12 parts of curing agent, 100-140 parts of deionized water; The antistatic agent is prepared by the following method: S1: Polyethylene glycol dioxirane methyl ether and 2-(methacrylate)ethyl 3,5-diaminobenzoic acid react under the catalysis of glacial acetic acid to form a polymer; S2: Under nitrogen protection, the polymer reacts with 3-(dimethylamino)-1-propanethiol under the action of initiator AIBN to form a tertiary amine-terminated polymer; S3: The terminal tertiary amine polymer reacts with dodecane bromide to obtain an antistatic agent.

2. The impact-resistant industrial coating according to claim 1, characterized in that: In step S1, the molar ratio of polyethylene glycol dioxirane methyl ether to 2-(methacrylate)ethyl 3,5-diaminobenzoic acid is 1:(1-1.5).

3. The impact-resistant industrial coating according to claim 1, characterized in that: In step S2, the feed mass ratio of the polymer to 3-(dimethylamino)-1-propanethiol is (8-15):

2.

4. The impact-resistant industrial coating according to claim 1, characterized in that: In step S3, the feed mass ratio of the terminal tertiary amine polymer to dodecane bromide is (3-5):

1.

5. The impact-resistant industrial coating according to claim 1, characterized in that: The modified thickener is prepared by the following method: S1: Glyceric acid and propylene glycol react under the catalysis of p-toluenesulfonic acid to form hyperbranched polyester; S2: Under nitrogen protection, toluene 2,6-diisocyanate and PEG800 reacted under the catalysis of dibutyltin dilaurate to obtain a polyurethane prepolymer; then octadecylamine polyoxyethylene ether was added to carry out a chain extension reaction to obtain a long-chain grafted polyurethane; S3: Under nitrogen protection, long-chain grafted polyurethane reacts with hyperbranched polyester to obtain a modified thickener.

6. The impact-resistant industrial coating according to claim 5, characterized in that: In step S1, the molar ratio of glyceric acid to propylene glycol is (9-12):

1.

7. The impact-resistant industrial coating according to claim 5, characterized in that: In step S2, the mass ratio of toluene 2,6-diisocyanate, PEG800 and octadecylamine polyoxyethylene ether is 1:(3-5):(2-3).

8. The impact-resistant industrial coating according to claim 5, characterized in that: In step S3, the feed mass ratio of the long-chain grafted polyurethane and the hyperbranched polyester is (5-10):

1.

9. The impact-resistant industrial coating according to claim 1, characterized in that: The leveling agent is one of polyether modified polysiloxane and polyester modified polysiloxane; the dispersant is one of sodium dodecyl sulfate and sodium dodecylbenzene sulfonate; the antioxidant is one of antioxidant 1010, antioxidant 1076, and antioxidant 168; the curing agent is one of phthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

10. A method for producing an impact-resistant industrial coating according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Weighing by weight: 80-100 parts of epoxy resin, 2-5 parts of graphene oxide, 3-5 parts of antistatic agent, 5-8 parts of modified thickener, 1-3 parts of dispersant, 0.5-1.5 parts of leveling agent, 2-3 parts of antioxidant, 8-12 parts of curing agent, and 100-140 parts of deionized water; (2) Add deionized water, epoxy resin, graphene oxide, dispersant, and antioxidant to the stirrer in sequence and stir for 10-30 minutes; then add leveling agent, curing agent, and modified thickener and stir for 10-30 minutes; finally, add antistatic agent and stir until well mixed to obtain impact-resistant industrial coating.