An impact-resistant industrial coating and its manufacturing method

Abstract

This invention discloses an impact-resistant industrial coating and its manufacturing method, relating to the field of industrial coating technology. The impact-resistant industrial coating comprises the following raw materials in parts by weight: 80-100 parts epoxy resin, 2-5 parts graphene oxide, 3-5 parts antistatic agent, 5-8 parts modified thickener, 1-3 parts dispersant, 0.5-1.5 parts leveling agent, 2-3 parts antioxidant, 8-12 parts curing agent, and 100-140 parts deionized water. This invention involves reacting polyethylene glycol diethylene oxide methyl ether with 2-(methacrylate) ethyl ester and 3,5-diaminobenzoic acid to generate a polymer; reacting the polymer with 3-(dimethylamino)-1-propanethiol to generate a terminal tertiary amine polymer; and reacting the terminal tertiary amine polymer with dodecane bromo to undergo a quaternization reaction to obtain the antistatic agent. The impact-resistant industrial coating prepared by this invention exhibits excellent antistatic and rheological properties.

Description

Technical Field

[0001] This invention relates to the field of industrial coatings technology, specifically to an impact-resistant industrial coating and its manufacturing method. Background Technology

[0002] In modern industry, with the rapid development of manufacturing and the increasing demands on material performance, industrial coatings, as important materials for protecting and decorating various industrial products, directly affect the product's service life and quality stability. Impact-resistant industrial coatings, as a key protective material, have received widespread attention in recent years.

[0003] With the rapid development of high-precision and high-sensitivity industries such as electronics, electrical appliances, aerospace, and chemicals, more stringent requirements have been placed on the impact resistance of industrial coatings. In practical applications, static electricity generated on the coating surface can cause various problems, such as hindering production, generating sparks leading to explosions, and damaging integrated circuits in electronic devices. The method for eliminating static electricity is generally 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 achieve the purpose of antistatic action by forming leakage charge channels through ionic conduction or hygroscopic effects of ionized or polar groups. Commonly used antistatic agents include quaternary ammonium salts and alkyl phosphates. In the field of industrial coatings, the optimization of rheological properties is also crucial for improving the overall performance of coatings. Rheological properties not only affect the storage stability, application performance, and final coating quality 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, developing an industrial coating with excellent rheological and antistatic properties has become an urgent task.

[0004] Chinese invention patent CN118956221A discloses a weather-resistant industrial coating and its preparation method. The patent describes a process involving the reaction of 6-chloro-1-hexene and 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide to obtain a hexenyl UV absorber; the reaction of the hexenyl UV absorber, methacrylic acid, and bisphenol A type epoxy resin E51 to obtain a modified epoxy resin emulsion; the polymerization and growth of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dioxide and methylphenylsilanediol on pre-modified glass flakes to obtain modified glass flakes; and the uniform mixing of the modified epoxy resin emulsion, modified glass flakes, self-healing curing agent, and defoamer to obtain the weather-resistant industrial coating. This industrial coating exhibits excellent anti-aging properties, but its antistatic properties are poor. Summary of the Invention

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

[0006] To achieve the above objectives, the present invention provides the following technical solution:

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

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

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

[0010] S1: Polyethylene glycol diethylene oxide methyl ether, 2-(methacrylate) ethyl ester, and 3,5-diaminobenzoic acid react to form a polymer under the catalysis of glacial acetic acid;

[0011] S2: Under nitrogen protection, the polymer reacts with 3-(dimethylamino)-1-propanethiol in the presence of initiator AIBN to generate a terminal tertiary amine polymer.

[0012] S3: The antistatic agent is obtained by reacting the terminal tertiary amine polymer with bromododecane.

[0013] In step S1, the molar ratio of polyethylene glycol diethylene oxide methyl ether and 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid is 1:(1-1.5).

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

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

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

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

[0018] 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-linked polyurethane.

[0019] S3: Nitrogen protection, long-linked branched polyurethane reacts with hyperbranched polyester to obtain a modified thickener.

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

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

[0022] In step S3, the mass ratio of the long-linked branched polyurethane to the hyperbranched polyester 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 dodecylbenzene sulfonate; the antioxidant is one of antioxidant 1010, antioxidant 1076 and antioxidant 168; and the curing agent is one of phthalic anhydride, hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

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

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

[0026] (2) Add deionized water, epoxy resin, graphene oxide, dispersant and antioxidant to the mixer 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.

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

[0028] (1) In this invention, a polymer is generated by reacting the epoxy group in polyethylene glycol diethylene oxide methyl ether with the amino group in 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid; the double bond in the polymer reacts with the thiol group in 3-(dimethylamino)-1-propanethiol in a thiol-ene click reaction to generate a terminal tertiary amine polymer; the terminal tertiary amine polymer undergoes a quaternization reaction with bromododecane to obtain an antistatic agent.

[0029] (2) The amino and epoxy groups in the antistatic agent 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid prepared in this invention react to form a three-dimensional network structure, which improves solvent resistance and thermal stability; the terminal tertiary amine polymer reacts with bromododecane to form a cationic quaternary ammonium salt, which neutralizes static charge through ionic conductivity; the long-chain dodecyl enhances hydrophobicity, making the quaternary ammonium salt easy to migrate to the coating surface and accumulate, thus improving antistatic durability; 3-(dimethylamino)-1-propanethiol introduces thioether bonds, which relieves internal stress in the coating, resists oxidation and hydrolysis, and prolongs the antistatic life.

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

[0031] (4) The modified thickener prepared in this invention has a hyperbranched structure, which reduces intermolecular entanglement in solution, resulting in good flowability and low viscosity. It thickens rapidly at low shear rates, while its viscosity decreases rapidly at high shear rates, exhibiting good shear-thinning behavior. This rheological property makes the system containing the modified thickener easier to operate during construction, less prone to sagging, and maintains good consistency when stationary, preventing the precipitation of solid components such as pigments. Detailed Implementation

[0032] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0033] Example 1: Preparation of antistatic agent:

[0034] S1: Add 200 ml DMF, 0.1 mol polyethylene glycol diethylene oxide methyl ether, and 0.1 mol 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid to the reactor, stir and mix well, heat to 80℃, then add 6 g glacial acetic acid, react for 6 h, cool to room temperature, add 50 ml deionized water to dilute, distill under reduced pressure at 80℃ for 4 h, add 100 ml 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 anhydrous sodium sulfate, stir and dry for 2 h, concentrate under reduced pressure at 40℃ for 2 h; add the concentrate dropwise to 300 ml ice-cold diethyl ether and stir to precipitate the polymer, filter through a Buchner funnel and wash three times with diethyl ether (40 ml each time), and finally dry under vacuum at 40℃ for 24 h to obtain the polymer;

[0035] S2: Under nitrogen protection, 1200 ml DMSO, 40 g 3-(dimethylamino)-1-propanethiol, and 160 g polymer were added to the reactor and stirred. Then, 5 g initiator AIBN was added, the temperature was raised to 60 °C, and the reaction was carried out for 12 h. After that, the mixture was distilled under reduced pressure at 70 °C for 5 h. The concentrated liquid was added dropwise to 500 ml of ice-cold diethyl ether and stirred to precipitate the polymer. The polymer was filtered through a Buchner funnel and washed three times with diethyl ether (80 ml each time). The polymer was then dried under vacuum at 50 °C for 24 h to obtain the tertiary amine polymer.

[0036] S3: Add 1000ml toluene and 90g terminal tertiary amine polymer to the reactor, stir and mix well, then slowly add 30g bromododecane dropwise over 10min. After the addition is complete, reflux the reaction for 5h, then distill under reduced pressure at 65℃ for 4h. Recrystallize three times with a mixture of acetone / ethanol (acetone / ethanol (V / V) = 9:1) (using 300ml of the mixture each time), and dry under vacuum at 60℃ for 5h to obtain the antistatic agent.

[0037] Example 2: Preparation of antistatic agent:

[0038] S1: Add 200 ml DMF, 0.1 mol polyethylene glycol diethylene oxide methyl ether, and 0.12 mol 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid to the reactor, stir to mix, heat to 90℃, then add 7 g glacial acetic acid, react for 5 h, cool to room temperature, add 50 ml deionized water to dilute, distill under reduced pressure at 80℃ for 4 h, add 100 ml 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 anhydrous sodium sulfate, stir and dry for 2 h, concentrate under reduced pressure at 40℃ for 2 h; drop the concentrate into 300 ml ice-cold ether and stir to precipitate polymer, filter through a Buchner funnel and wash three times with ether (40 ml each time), finally dry under vacuum at 40℃ for 24 h to obtain polymer;

[0039] S2: Under nitrogen protection, 1500 ml DMSO, 40 g 3-(dimethylamino)-1-propanethiol, and 240 g polymer were added to the reactor and stirred. Then, 5 g initiator AIBN was added, the temperature was raised to 70 °C, and the reaction was carried out for 10 h. After that, the mixture was distilled under reduced pressure at 70 °C for 5.5 h. The concentrate was dropped into 700 ml of ice-cold diethyl ether and stirred to precipitate the polymer. The polymer was filtered through a Buchner funnel and washed three times with diethyl ether (80 ml each time). The polymer was then dried under vacuum at 50 °C for 24 h to obtain the tertiary amine polymer.

[0040] S3: Add 1000ml toluene and 120g terminal tertiary amine polymer to the reactor, stir and mix well, then slowly add 30g bromododecane dropwise over 10min. After the addition is complete, reflux the reaction for 6h, then distill under reduced pressure at 50℃ for 3h. Recrystallize three times with a mixture of acetone / ethanol (acetone / ethanol (V / V) = 9:1) (using 400ml of the mixture each time), and dry under vacuum at 70℃ for 4h to obtain the antistatic agent.

[0041] Example 3: Preparation of antistatic agent:

[0042] S1: Add 200 ml DMF, 0.1 mol polyethylene glycol diethylene oxide methyl ether, and 0.15 mol 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid to the reactor, stir to mix, heat to 100℃, then add 8 g glacial acetic acid, react for 4 h, cool to room temperature, add 50 ml deionized water to dilute, distill under reduced pressure at 80℃ for 4 h, add 100 ml 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 anhydrous sodium sulfate, stir and dry for 2 h, concentrate under reduced pressure at 40℃ for 2 h; add the concentrate dropwise to 300 ml ice-cold diethyl ether and stir to precipitate the polymer, filter through a Buchner funnel and wash three times with diethyl ether (40 ml each time), finally dry under vacuum at 40℃ for 24 h to obtain the polymer;

[0043] S2: Under nitrogen protection, 1600 ml DMSO, 40 g 3-(dimethylamino)-1-propanethiol, and 300 g polymer were added to the reactor and stirred. Then, 5 g initiator AIBN was added, the temperature was raised to 80 °C, and the reaction was carried out for 8 h. After that, the mixture was distilled under reduced pressure at 70 °C for 6 h. The concentrated liquid was added dropwise to 700 ml of ice-cold diethyl ether and stirred to precipitate the polymer. The polymer was filtered through a Buchner funnel and washed three times with diethyl ether (80 ml each time). The polymer was then dried under vacuum at 50 °C for 24 h to obtain the tertiary amine polymer.

[0044] S3: Add 1000ml toluene and 150g terminal tertiary amine polymer to the reactor, stir and mix well, then slowly add 30g bromododecane dropwise over 10min. After the addition is complete, reflux the reaction for 7h, then distill under reduced pressure at 60℃ for 2h. Recrystallize three times with a mixture of acetone / ethanol (acetone / ethanol (V / V) = 9:1) (using 400ml of the mixture each time), and dry under vacuum at 80℃ for 3h to obtain the antistatic agent.

[0045] Example 4: Preparation of modified thickener:

[0046] S1: Under nitrogen protection, 400 ml of toluene, 0.9 mol of glyceric acid, and 0.1 mol of glycerol were added to the reactor and stirred until homogeneous. Then, 8 g of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 6 hours (water generated during the reaction was removed using a water separator). The mixture was then cooled to room temperature, and 5 wt% saturated sodium bicarbonate solution was slowly added to adjust the pH to neutral (neutral in this application is pH = 7). The mixture was stirred thoroughly for 30 minutes, allowed to stand and separate into layers, and the organic phase was transferred to a rotary evaporator. The mixture was distilled under reduced pressure at 70°C for 3 hours and then dried under vacuum at 70°C for 5 hours to obtain hyperbranched polyester.

[0047] S2: Under nitrogen protection, 500 ml DMF and 10 g toluene 2,6-diisocyanate were added to the reactor and stirred to dissolve. The temperature was raised to 50 °C, and then 30 g PEG800 was slowly added dropwise over 20 min. After the addition was complete, 3 g dibutyltin dilaurate was added, and the reaction was carried out for 6 h to obtain a polyurethane prepolymer. Then, 20 g octadecylamine polyoxyethylene ether was added, and the reaction was continued for 4 h. After that, 800 ml ice water was added to precipitate the polyurethane, which was then filtered and dried under vacuum at 50 °C for 6 h to obtain a long-linked polyurethane.

[0048] S3: Under nitrogen protection, add 600ml DMF, 50g long-linked branched polyurethane, and 10g hyperbranched polyester to the reactor, stir and mix well, heat to 70℃, then add 5g dibutyltin dilaurate, react for 4h, distill under reduced pressure at 70℃ for 3h, and vacuum dry at 70℃ for 5h to obtain the modified thickener.

[0049] Example 5: Preparation of modified thickener:

[0050] S1: Under nitrogen protection, add 500 ml toluene, 1.0 mol glyceric acid, and 0.1 mol glycerol to the reactor and stir until homogeneous. Then add 8 g p-toluenesulfonic acid and heat to reflux for 8 h (use a water separator to remove the generated water during the reaction). After cooling to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral. Stir thoroughly for 30 min, allow to stand and separate into layers, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry under vacuum at 70 °C for 5 h to obtain hyperbranched polyester.

[0051] S2: Under nitrogen protection, 500 ml DMF and 10 g toluene 2,6-diisocyanate were added to the reactor and stirred to dissolve. The temperature was raised to 60°C, and then 40 g PEG800 was slowly added dropwise over 20 min. After the addition was complete, 3 g dibutyltin dilaurate was added, and the reaction was carried out for 5 h to obtain a polyurethane prepolymer. Then 25 g octadecylamine polyoxyethylene ether was added, and the reaction was continued for 5 h. The temperature was lowered to room temperature, 800 ml ice water was added to precipitate, filtered, and vacuum dried at 50°C for 6 h to obtain a long-linked polyurethane.

[0052] S3: Under nitrogen protection, add 600ml DMF, 80g long-linked branched polyurethane, and 10g hyperbranched polyester to the reactor, stir and mix well, heat to 80℃, then add 5g dibutyltin dilaurate, react for 3h, distill under reduced pressure at 70℃ for 3h, and vacuum dry at 70℃ for 5h to obtain the modified thickener.

[0053] Example 6: Preparation of modified thickener:

[0054] S1: Under nitrogen protection, add 600 ml toluene, 1.2 mol glyceric acid, and 0.1 mol glycerol to the reactor and stir until homogeneous. Then add 8 g p-toluenesulfonic acid and heat to reflux for 10 h (use a water separator to remove the generated water during the reaction). After cooling to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral. Stir thoroughly for 30 min, allow to stand and separate into layers, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry under vacuum at 70 °C for 5 h to obtain hyperbranched polyester.

[0055] S2: Under nitrogen protection, 500 ml DMF and 10 g toluene 2,6-diisocyanate were added to the reactor and stirred to dissolve. The temperature was raised to 70°C, and then 50 g PEG800 was slowly added dropwise over 20 min. After the addition was complete, 4 g dibutyltin dilaurate was added, and the reaction was carried out for 4 h to obtain a polyurethane prepolymer. Then, 30 g octadecylamine polyoxyethylene ether was added, and the reaction was continued for 6 h. The temperature was lowered to room temperature, 800 ml ice water was added to precipitate, filtered, and vacuum dried at 50°C for 6 h to obtain a long-linked polyurethane.

[0056] S3: Under nitrogen protection, add 600ml DMF, 100g long-linked branched polyurethane, and 10g hyperbranched polyester to the reactor, stir and mix well, heat to 90℃, then add 5g dibutyltin dilaurate, react for 2h, distill under reduced pressure at 70℃ for 4h, and vacuum dry at 70℃ for 5h to obtain the modified thickener.

[0057] Example 7: Preparation of impact-resistant industrial coatings:

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

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

[0060] Example 8: Preparation of impact-resistant industrial coatings:

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

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

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

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

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

[0066] Comparative Example 1

[0067] The 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 equal weight of an antistatic agent 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-(methacrylate) ethyl 3,5-diaminobenzoic acid in step S1 is replaced with an equal weight of 2-aminostyrene.

[0069] Comparative Example 2

[0070] The 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 equal weight of an antistatic agent prepared by the following method:

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

[0072] Comparative Example 3

[0073] The 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 equal weight of an antistatic agent prepared by the following method:

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

[0075] Comparative Example 4

[0076] The 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 equal weight of an antistatic agent prepared by the following method:

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

[0078] Comparative Example 5

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

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

[0081] Comparative Example 6

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

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

[0084] Comparative Example 7

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

[0086] The preparation method of the modified thickener is basically the same as that in 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 method for manufacturing an impact-resistant industrial coating is basically the same as that in 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 toluene, 1.0 mol glyceric acid, and 0.1 mol glycerol to the reactor and stir until homogeneous. Then add 8 g p-toluenesulfonic acid and heat to reflux for 8 h (use a water separator to remove the generated water during the reaction). After cooling to room temperature, slowly add 5 wt% saturated sodium bicarbonate solution to adjust the pH to neutral. Stir thoroughly for 30 min, allow to stand and separate into layers, transfer the organic phase to a rotary evaporator, distill under reduced pressure at 70 °C for 3 h, and dry under vacuum at 70 °C for 5 h to obtain hyperbranched polyester.

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

[0091] Under nitrogen protection, 500 ml DMF and 10 g toluene 2,6-diisocyanate were added to the reactor and stirred to dissolve. The temperature was raised to 60 °C, and then 40 g PEG800 was slowly added dropwise over 20 min. After the addition was complete, 3 g dibutyltin dilaurate was added and the reaction was carried out for 5 h. The temperature was lowered to room temperature, 800 ml ice water was added to precipitate the product, and the mixture was filtered. The product was then vacuum dried at 50 °C for 6 h to obtain the polyurethane prepolymer.

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

[0093] Comparative Example 9

[0094] A weather-resistant industrial coating is prepared using the raw material composition, proportioning and method of Example 2 of Chinese Invention Patent Publication No. CN118956221A.

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

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

[0097] According to GB / T 33328-2016, the surface resistivity of industrial coatings was tested using a ZC36 high-resistivity meter in a specific environment (temperature 23℃, relative humidity 50%), with the test voltage set to 500V DC.

[0098] Thixotropic index of industrial coatings was tested using a rotational viscometer: In accordance with GB / T2794-2022, an NDJ-4 type rotational viscometer was used, with two speed settings (6 r / min and 60 r / min) selected, to 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] As can be seen from Table 1, the industrial coating prepared in this application has good antistatic and rheological properties.

[0102] Comparative Example 1 is a comparative example in which 2-(methacrylate) ethyl ester 3,5-diaminobenzoic acid in step S1 of the antistatic agent preparation process is replaced with 2-aminostyrene; Comparative Example 2 is a comparative example in which polyethylene glycol diglycidyl ether in step S1 of the antistatic agent preparation process is replaced with 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 with 3-dimethylamino-1-propanol; and Comparative Example 4 is a comparative example in which bromododecane in step S3 of the antistatic agent preparation process is replaced with bromobutane. As can be seen from Table 1, the antistatic effect is not as good as that of this application. This is because the polyethylene glycol segments in the main chain endow the polymer with excellent flexibility and hydrophilicity. During the coating film formation process, the flexible segments help the antistatic agent to be uniformly dispersed in the coating, avoiding phase separation due to excessive rigidity. The amino group in 2-(methacrylate) ethyl ester and 3,5-diaminobenzoic acid reacts with the epoxy group in polyethylene glycol diethylene oxide methyl ether to form a three-dimensional network structure, improving the solvent resistance and thermal stability of the antistatic agent and preventing performance degradation due to high temperature or solvent corrosion. The tertiary amine polymer undergoes a quaternization reaction with bromododecane to form a cationic quaternary ammonium salt. This cation can adsorb anions from the environment to form an electrical double layer, rapidly neutralizing static charge through ionic conductivity. The introduction of long-chain dodecyl groups enhances hydrophobicity, making it easier for the quaternary ammonium salt to migrate to and accumulate on the coating surface, improving antistatic durability. The introduction of 3-(dimethylamino)-1-propanethiol introduces thioether bonds. The flexibility and chemical stability of these bonds alleviate internal stress during coating curing, preventing the antistatic agent from failing due to brittle fracture. Simultaneously, the thioether bonds possess antioxidant and hydrolysis-resistant properties, slowing down the decomposition of the quaternary ammonium salt in humid environments and extending the antistatic lifespan.

[0103] Comparative Example 5 is a comparison example where glyceric acid in step S1 of the modified thickener preparation process is replaced with 3-hydroxypropionic acid; Comparative Example 6 is a comparison example where glycerol in step S1 of the modified thickener preparation process is replaced with pentaerythritol; Comparative Example 7 is a comparison example where octadecylamine polyoxyethylene ether in step S2 of the modified thickener preparation process is replaced with dodecylamine polyoxyethylene (5) ether; and Comparative Example 8 is a comparison example where no octadecylamine polyoxyethylene ether is added during the preparation of the modified thickener. As can be seen from Table 1, this is because the hyperbranched polyester formed by the condensation polymerization of glyceric acid and glycerol has a large number of terminal hydroxyl groups in its three-dimensional dendritic structure, forming a dense intermolecular hydrogen bond network. This high-density polar group significantly increases the structural viscosity of the system, giving the coating excellent thixotropic recovery properties. Compared with linear thickeners, the rigid skeleton of the hyperbranched core can maintain part of the network structure under shear force, reducing viscosity collapse under high shear rates. The polyurethane prepolymer formed by PEG800 and toluene diisocyanate introduces octadecyl hydrophobic long chains through chain extension, which form physical micelles in the coating through hydrophobic association, further strengthening the network structure. The micelles are stable in a static state and dissociate under shear stress, achieving significant thixotropy and effectively balancing storage stability. The hydroxyl groups of the hyperbranched polyester form reversible hydrogen bonds with the urethane groups (-NHCOO-) in the polyurethane. This dynamic network partially dissociates during application shearing and rapidly recombines at rest, achieving a balance between shear thinning and thixotropy. The terminal hydroxyl groups of the hyperbranched polyester react with the isocyanate groups (-NCO) of the polyurethane to form stable urethane bonds (-NHCOO-), constructing a hyperbranched-linear hybrid network. This chemical bonding avoids interphase separation, 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 using the raw material composition, proportion, and method of Example 2 of Chinese Invention Patent Publication No. CN118956221A. Its antistatic properties and rheological properties are not as good as those of this application.

[0105] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

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

2. The impact-resistant industrial coating according to claim 1, characterized in that, In step S1, the molar ratio of polyethylene glycol diethylene oxide methyl ether and 2-(methacrylate) ethyl ester 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 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 mass ratio of the terminal tertiary amine polymer to bromododecane 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 glycerol 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-linked branched polyurethane. S3: Nitrogen protection, long-linked branched 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 glycerol 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 mass ratio of the long-linked branched polyurethane to 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; and the curing agent is one of phthalic anhydride, hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

10. A method for manufacturing an impact-resistant industrial coating according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 80-100 parts epoxy resin, 2-5 parts graphene oxide, 3-5 parts antistatic agent, 5-8 parts modified thickener, 1-3 parts dispersant, 0.5-1.5 parts leveling agent, 2-3 parts antioxidant, 8-12 parts curing agent, and 100-140 parts deionized water; (2) Add deionized water, epoxy resin, graphene oxide, dispersant and antioxidant to the mixer 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.