Radiation-cured coating and environmentally friendly method for its preparation

Abstract

The application discloses a kind of radiation curing coating, the radiation curing coating is modified urethane acrylate;1,6-hexanediol diacrylate 10-20 parts, active diluent 15-20 parts, silane coupling agent KH570 1-3 parts, benzophenone photoinitiator 1-3 parts, carbon black 1-3 parts, polyethylene glycol (molecular weight less than 2500) 1-3 parts are added to urethane acrylate environmentally-friendly preparation method product, 3 (ethoxy) trimethylolpropane tri (methyl) acrylate EO-TMPTA, 2EO-TMPTA, 3EO TMPTA are stirred and uniformly mixed, finally UV ultraviolet irradiation is cured, light radiation energy 2000-3000 mJ / cm2, modified urethane acrylate can be obtained.The radiation curing coating of the application can realize UV curing and electron beam curing, the urethane acrylate prepared by the environmentally-friendly preparation method is used as the base material, cooperates with 1,6-hexanediol diacrylate raw material, and is cooperated with graphene adjusted nanosilica agent and magnesium oxide modifier, and is synergistic.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating, in particular to a radiation-cured coating and an environmentally-friendly preparation method thereof. BACKGROUND

[0002] Traditional preparation of urethane needs to use isocyanate, and when preparing radiation-curable urethane (meth) acrylic polyester monomer, oligomer or high molecular polymer, the traditional manufacturing method adopts polyol, isocyanate and (meth) acrylic hydroxyethyl, propyl or butyl ester for preparation. The use of existing isocyanate, on the one hand, leads to high cost, and on the other hand, isocyanate is a toxic and hazardous chemical, and production, storage and transportation all bring safety and environmental risks, especially in today's increasing environmental pressure, the use of isocyanate such as TDI, MDI, IPDI or HDI will be limited by many transportation, storage and environmental approvals; using relatively more environmentally friendly raw materials and chemical synthesis method, preparing urethane polyol by reacting cyclic carbonate with organic amine, and then preparing radiation-curable urethane (meth) acrylic polyester by catalytic ester exchange reaction or esterification reaction, the cost is low, however, the radiation-cured coating uses raw materials containing urethane acrylate, the wear resistance of the product is poor, and the impact toughness and wear resistance of the product are difficult to coordinate and improve, which limits the use of the product, based on this, the present application further improves the treatment. SUMMARY

[0003] In view of the defects of the prior art, the present application aims to provide a radiation-cured coating and an environmentally-friendly preparation method thereof to solve the problems raised in the background art.

[0004] The technical problem solved by the present application adopts the following technical solution:

[0005] The present application provides a radiation-cured coating, the cured coating is a modified urethane acrylate;

[0006] The specific modification method is:

[0007] S1. 120-125 parts by weight of monoethanolamine is added to a 500 mL four-necked flask, protected by nitrogen, continuously stirred, heated to 40-50℃, and 175-177 parts by weight of ethylene carbonate is slowly added dropwise, added for half an hour, and continuously incubated at 50℃ for 3-4 hours until the monoethanolamine is completely consumed, and the reaction formula is as follows:

[0008] ;

[0009] S2. Synthesis of urethane (meth) acrylic polyester: 1 mole of product of step S1. and 0.1 gram of N, N-dinaphthyl-p-phenylenediamine and 3 milliliters of 2.5% lithium hydroxide methanol solution are added into a 500 milliliter four-necked flask, a reflux condenser is installed, 200-218 parts by weight of methyl methacrylate is added, a polymerization inhibitor hydroquinone monomethyl ether is added under continuous stirring, and heated to 115-120℃, and continuously stirred for 4 hours of reaction, and 98.3% of the theoretical value of methanol is collected and distilled off, and it is ready;

[0010] S3. To the product of S2, 10-20 parts of 1, 6-hexanediol diacrylate, 5-10 parts of graphene-regulated nano-silica agent, 4-7 parts of magnesium oxide modifier, 15-20 parts of active diluent, 1-3 parts of silane coupling agent KH570, 1-3 parts of benzophenone photoinitiator, 1-3 parts of carbon black, 1-3 parts of polyethylene glycol with a molecular weight less than 2500, 3EO-TMPTA, stirring and mixing, and finally UV ultraviolet irradiation curing, light radiation energy 2000-3000 mJ / cm 2 , and the modified urethane acrylate is obtained.

[0011] Preferably, the preparation method of the graphene-regulated nano-silica agent is:

[0012] S01: The nano-silica is first heat treated at 210-230℃ for 10-15 min, then cooled to 65-70℃ at a rate of 1-3℃ / min, and treated at constant temperature to obtain the nano-silica treated at constant temperature;

[0013] S02: 3-5 parts of the nano-silica treated at constant temperature, 1-2 parts of lanthanum chloride solution, 2-4 parts of sodium dodecyl benzene sulfonate solution, and 0.35-0.55 parts of titanate coupling agent are stirred and mixed to obtain a nano-silica liquid;

[0014] S03: The graphene is immersed in a sodium silicate solution of 3-5 times the volume of the graphene for primary immersion treatment, then suction filtered and dried, and then immersed in a yttrium nitrate solution of 2-5 times the volume of the graphene for secondary immersion treatment, and after the immersion is completed, suction filtered and dried to obtain a graphene modifier;

[0015] S04: The graphene modifier and the nano-silica liquid are ball milled according to a weight ratio of 5:2, and after the ball milling is completed, washed with water and dried to obtain the graphene-regulated nano-silica agent.

[0016] Preferably, the mass fraction of the lanthanum chloride solution is 2-5%, and the mass fraction of the sodium dodecyl benzene sulfonate solution is 10-15%.

[0017] Preferably, the pressure of the primary immersion treatment is 5-10 MPa, and the immersion time is 20-30 min; the pressure of the secondary immersion treatment is 15-20 MPa, and the immersion time is 5-10 min.

[0018] Preferably, the mass fraction of the sodium silicate solution is 4-8%, and the mass fraction of the yttrium nitrate solution is 2-5%.

[0019] Preferably, the ball milling speed of the ball milling treatment is 1000-1500 r / min, and the ball milling time is 1-2 h.

[0020] Preferably, the preparation method of the magnesium oxide modifier is as follows:

[0021] S101: irradiate the magnesium oxide in a proton irradiation box for 10-15 min at an irradiation power of 300-350 W, and obtain an irradiation agent after the irradiation is completed;

[0022] S102: add 2-5 parts of the irradiation agent to 5-10 parts of a chitosan solution, then add 1-2 parts of sodium lignosulfonate and 0.35-0.55 parts of a nano silicon sol, and ultrasonically treat for 1-2 h at an ultrasonic power of 220-240 W; after the ultrasonic treatment is completed, wash with water and dry to obtain a magnesium oxide modifier.

[0023] Preferably, the mass fraction of the chitosan solution is 3-5%.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] The radiation-cured coating of the present application can be UV-cured and electron beam-cured, and the urethane acrylate prepared by the environmentally friendly preparation method is used as the base material, the urethane acrylate has excellent environmental performance, and meanwhile, the 1,6-hexanediol diacrylate raw material is used, the graphene-regulated nano-silicon dioxide agent and the magnesium oxide modifier are matched and synergized, the present application has the following innovative points: the graphene has a sheet structure and can play a bearing effect, and the nano-silicon dioxide has a high specific surface area structure, so that the two are modified by the present application, the interface reaction effect of the system raw materials is enhanced, and the system bonding strength is optimized, the magnesium oxide modifier plays a reinforcing effect in the system, fills the system structure, and synergizes with the graphene-regulated nano-silicon dioxide agent to enhance the effect, and with the assistance of the carbon black, the polyethylene glycol (molecular weight 1000), 3(ethoxy)trimethylolpropane trimethyl acrylate 3EO-TMPTA, and benzophenone photoinitiator, the wear resistance and impact toughness of the product are coordinately improved. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0027] The radiation-cured coating material in the embodiment is a modified urethane acrylate;

[0028] The specific modification method is as follows:

[0029] S1. 120-125 parts by weight of monoethanolamine are added into a 500 mL four-necked flask, nitrogen protection is performed, continuous stirring is performed, heating is performed to 40-50 DEG C, 175-177 parts by weight of ethylene carbonate is slowly added dropwise, half an hour is added, 50 DEG C is continuously kept, reaction is performed for 3-4 hours, until monoethanolamine is completely consumed, and the reaction formula is as follows:

[0030] ;

[0031] S2. The synthesis of the urethane (methyl) acrylate polyester: 1 mole of the product of step S1. and 0.1 gram of N, N-dinaphthyl-p-phenylenediamine and 3 milliliters of 2.5% lithium hydroxide methanol solution are added into a 500 milliliter four-necked flask, a reflux condenser is installed, 200-218 parts by weight of methyl methacrylate is added, an inhibitor hydroquinone monomethyl ether is added under continuous stirring, heating is performed to 115-120 DEG C, continuous stirring is performed, reaction is performed for 4 hours, and 98.3% of the theoretical value of methanol is collected and distilled out, and the modified urethane acrylate is obtained.

[0032] S3. 10-20 parts of 1, 6-hexanediol diacrylate, 5-10 parts of the graphene-regulated nano-silica agent, 4-7 parts of magnesium oxide modifier, 15-20 parts of active diluent, 1-3 parts of silane coupling agent KH570, 1-3 parts of benzophenone photoinitiator, 1-3 parts of carbon black, 1-3 parts of polyethylene glycol with a molecular weight less than 2500, and 3EO-TMPTA are added into the product of S2, stirring is uniformly performed, finally, UV ultraviolet irradiation curing is performed, and the light radiation energy is 2000-3000 mJ / cm 2 , and the modified urethane acrylate is obtained.

[0033] The preparation method of the graphene-regulated nano-silica agent in the embodiment is as follows:

[0034] S01: The nano-silica is first heat-treated at 210-230 DEG C for 10-15 min, then cooled to 65-70 DEG C at a rate of 1-3 DEG C / min, and kept at 65-70 DEG C, to obtain the kept nano-silica.

[0035] S02: 3-5 parts of the nano-silica, 1-2 parts of the lanthanum chloride solution, 2-4 parts of the sodium dodecyl benzene sulfonate solution and 0.35-0.55 parts of the titanate coupling agent were stirred and mixed to obtain a nano-silica solution;

[0036] S03: the graphene was immersed in a sodium silicate solution with a volume of 3-5 times of the graphene for a first immersion treatment, and then was subjected to suction filtration and drying, and then was immersed in a yttrium nitrate solution with a volume of 2-5 times of the graphene for a second immersion treatment, and then was subjected to suction filtration and drying to obtain a graphene modifier;

[0037] S04: the graphene modifier and the nano-silica solution were subjected to ball milling treatment at a weight ratio of 5:2, and then were subjected to water washing and drying to obtain a graphene-regulated nano-silica agent.

[0038] The mass fraction of the lanthanum chloride solution in the embodiment is 2-5%; and the mass fraction of the sodium dodecyl benzene sulfonate solution is 10-15%.

[0039] The pressure of the first immersion treatment in the embodiment is 5-10 MPa, and the immersion time is 20-30 min; and the pressure of the second immersion treatment is 15-20 MPa, and the immersion time is 5-10 min.

[0040] The mass fraction of the sodium silicate solution in the embodiment is 4-8%; and the mass fraction of the yttrium nitrate solution is 2-5%.

[0041] The ball milling speed of the ball milling treatment in the embodiment is 1000-1500 r / min, and the ball milling time is 1-2 h.

[0042] The preparation method of the magnesium oxide modifier in the embodiment is as follows:

[0043] S101: the magnesium oxide was subjected to proton irradiation in a proton irradiation box for 10-15 min at an irradiation power of 300-350 W to obtain an irradiation agent;

[0044] S102: 2-5 parts of the irradiation agent was added to 5-10 parts of a chitosan solution, and then 1-2 parts of sodium lignosulfonate and 0.35-0.55 parts of a nano-silica sol were added, and the mixture was subjected to ultrasonic treatment at an ultrasonic power of 220-240 W for 1-2 h, and then the mixture was subjected to water washing and drying to obtain a magnesium oxide modifier.

[0045] The mass fraction of the chitosan solution in the embodiment is 3-5%.

[0046] Embodiment 1.

[0047] The radiation-cured coating in the embodiment is a modified urethane acrylate;

[0048] The specific modification method is:

[0049] S1. 120 parts by weight of monoethanolamine are added to a 500 mL four-necked flask, protected by nitrogen, continuously stirred, heated to 40℃, and 175 parts by weight of ethylene carbonate is slowly added dropwise, which is completed in half an hour, and the reaction is continued at 50℃ for 3 hours until the monoethanolamine is completely consumed, and the reaction formula is as follows:

[0050]

[0051] S2. Synthesis of urethane (methyl) acrylate polyester: 1 gram mole of the product of step S1, 0.1 gram of N,N-dinaphthyl-p-phenylenediamine, and 3 milliliters of 2.5% lithium hydroxide methanol solution are added to a 500 milliliter four-necked flask, a reflux condenser is installed, 218 parts by weight of methyl methacrylate is added, a polymerization inhibitor hydroquinone monomethyl ether is added under continuous stirring, and heating is carried out to 115℃, and the reaction is continuously stirred for 4 hours, and 98.3% of the theoretical value of methanol is collected and distilled off, and it is ready.

[0052] S3. To the product of S2, 10 parts of 1,6-hexanediol diacrylate, 5 parts of graphene-regulated nano-silica agent, 4 parts of magnesium oxide modifier, 15 parts of active diluent, 1 part of silane coupling agent KH570, 1 part of benzophenone photoinitiator, 1 part of carbon black, 3 parts of polyethylene glycol 400, 3 parts of 2-ethoxytrimethylolpropane tri(meth)acrylate 2EO-TMPTA, are stirred and uniformly mixed, and finally UV ultraviolet irradiation curing is carried out, and the light radiation energy is 2000-3000 mJ / cm 2 , and the modified urethane acrylate ester is obtained.

[0053]

[0054] The preparation method of the graphene-regulated nano-silica agent of the embodiment is as follows:

[0055] S01: The nano-silica is first heat-treated at 210℃ for 10 min, then cooled to 65℃ at a rate of 1℃ / min, and heat-treated to obtain heat-treated nano-silica;

[0056] S02: 3 parts of heat-treated nano-silica, 1 part of lanthanum chloride solution, 2 parts of sodium dodecylbenzenesulfonate solution, and 0.35 parts of titanate coupling agent are stirred and uniformly mixed to obtain a nano-silica liquid;

[0057] S03: The graphene is immersed in a sodium silicate solution 3 times the volume of the graphene for primary immersion treatment, then suction filtered and dried, and then immersed in a yttrium nitrate solution 2 times the volume of the graphene for secondary immersion treatment, after which the immersion is completed, suction filtered and dried to obtain a graphene modifier;

[0058] ​​S04: The graphene modifier and the nanometer silica solution are ball milled according to a weight ratio of 5:2, and after the ball milling, water washing and drying are performed to obtain the graphene-regulated nanometer silica agent.

[0059] The lanthanum chloride solution has a mass fraction of 2%, and the sodium dodecyl benzene sulfonate solution has a mass fraction of 10%.

[0060] The pressure of the primary immersion treatment is 5 MPa, and the immersion time is 20 min; the pressure of the secondary immersion treatment is 15 MPa, and the immersion time is 5 min.

[0061] The sodium silicate solution has a mass fraction of 4%, and the yttrium nitrate solution has a mass fraction of 2%.

[0062] The ball milling speed of the ball milling treatment is 1000 r / min, and the ball milling time is 1 h.

[0063] The preparation method of the magnesium oxide modifier is as follows:

[0064] S101: The magnesium oxide is placed in a proton irradiation box and irradiated for 10 min at an irradiation power of 300 W, and after the irradiation, an irradiation agent is obtained;

[0065] S102: 2 parts of the irradiation agent are added to 5 parts of a chitosan solution, followed by adding 1 part of sodium lignosulfonate and 0.35 parts of a nanometer silicon sol, and then ultrasonic treatment is performed at an ultrasonic power of 220 W for 1 h, after which water washing and drying are performed to obtain a magnesium oxide modifier.

[0066] The chitosan solution has a mass fraction of 3%.

[0067] Example 2.

[0068] The radiation-cured coating of the present example is a modified urethane acrylate;

[0069] The specific modification method is as follows:

[0070] S1. 125 parts by weight of monoethanolamine are added to a 500 mL four-necked flask, nitrogen protection is performed, continuous stirring is performed, heating is performed to 50℃, 177 parts by weight of ethylene carbonate is slowly added dropwise, the addition is completed in half an hour, and the temperature is maintained at 50℃ for 4 hours until the monoethanolamine is completely consumed, and the reaction formula is as follows:

[0071] ;

[0072] S2. Synthesis of urethane (meth)acrylic polyester: 1 gram of product of step S1. and 0.1 gram of N,N-dinaphthyl-p-phenylenediamine and 3 milliliters of 2.5% lithium hydroxide methanol solution are added into a 500 milliliter four-necked flask, a reflux condenser is installed, 200 parts by weight of methyl methacrylate is added, a polymerization inhibitor hydroquinone monomethyl ether is added under continuous stirring, and heated to 120°C, and the reaction is continuously stirred for 4 hours, and 98.3% of the theoretical value of methanol is collected and distilled off, and the reaction is completed;

[0073] S3. 20 parts of 1,6-hexanediol diacrylate, 10 parts of graphene-regulated nano-silica agent, 7 parts of magnesium oxide modifier, 15-20 parts of active diluent, 3 parts of silane coupling agent KH570, 3 parts of carbon black, 3 parts of polyethylene glycol 600, and 5 parts of 3(ethoxy)trimethylolpropane tri(meth)acrylate 3EO-TMPTA are added into the product of S2, stirred and uniformly mixed, and electron beam irradiation curing is performed with a light radiation energy of 100 keV and an energy density of 300 kGy, and a modified urethane acrylate is obtained.

[0074] The preparation method of the graphene-regulated nano-silica agent of the embodiment is as follows:

[0075] S01: The nano-silica is first heat-treated at 230°C for 15 min, then cooled to 70°C at a rate of 3°C / min, and treated at constant temperature to obtain nano-silica treated at constant temperature;

[0076] S02: 5 parts of nano-silica treated at constant temperature, 2 parts of lanthanum chloride solution, 4 parts of sodium dodecyl benzene sulfonate solution, and 0.55 parts of titanate coupling agent are stirred and uniformly mixed to obtain a nano-silica liquid;

[0077] S03: The graphene is immersed in a sodium silicate solution 5 times as much as the graphene for first-stage immersion treatment, then suction-filtered, dried, immersed in a yttrium nitrate solution 5 times as much as the graphene for second-stage immersion treatment, suction-filtered and dried after the immersion is completed to obtain a graphene modifier;

[0078] S04: The graphene modifier and the nano-silica liquid are ball-milled according to a weight ratio of 5:2, and then washed with water and dried to obtain a graphene-regulated nano-silica agent.

[0079] The mass fraction of the lanthanum chloride solution of the embodiment is 5%; and the mass fraction of the sodium dodecyl benzene sulfonate solution is 15%.

[0080] The pressure of the first-stage immersion treatment of the embodiment is 10 MPa, and the immersion time is 30 min; and the pressure of the second-stage immersion treatment is 20 MPa, and the immersion time is 10 min.

[0081] The mass fraction of the sodium silicate solution of the embodiment is 8%; and the mass fraction of the yttrium nitrate solution is 5%.

[0082] The ball milling speed of the ball milling treatment of this embodiment is 1500 r / min, and the ball milling time is 2 h.

[0083] The preparation method of the magnesium oxide modifier of this embodiment is as follows:

[0084] S101: irradiate the magnesium oxide in a proton irradiation box for 15 min, the irradiation power is 350 W, and after the irradiation is completed, an irradiation agent is obtained;

[0085] S102: add 5 parts of the irradiation agent to 10 parts of a chitosan solution, then add 2 parts of sodium lignosulfonate and 0.55 parts of a nano silicon sol, ultrasonically treat for 2 h under an ultrasonic power of 240 W, and after the ultrasonic treatment is completed, wash with water and dry to obtain a magnesium oxide modifier.

[0086] The mass fraction of the chitosan solution of this embodiment is 5%.

[0087] Embodiment 3.

[0088] The radiation-cured coating of this embodiment is a modified urethane acrylate;

[0089] The specific modification method is as follows:

[0090] S1.122 parts by weight of monoethanolamine are added to a 500 mL four-necked flask, nitrogen protection is performed, continuous stirring is performed, heating is performed to 45℃, 176 parts by weight of ethylene carbonate is slowly added dropwise, the addition is completed in half an hour, and the temperature is continuously maintained at 50℃ for 3.5 hours until the monoethanolamine is completely consumed, and the reaction formula is as follows:

[0091]

[0092] S2. Synthesis of the urethane (methyl) acrylate polyester: 1 gram mole of the product of step S1., 0.1 gram of N,N-dinaphthyl-p-phenylenediamine, and 3 milliliters of 2.5% lithium hydroxide methanol solution are added to a 500 milliliter four-necked flask, a reflux condenser is installed, 219 parts by weight of methyl methacrylate is added, a polymerization inhibitor hydroquinone monomethyl ether is added under continuous stirring, heating is performed to 117℃, continuous stirring is performed for 4 hours, and 98.3% of the theoretical value of methanol is collected and distilled off, and the reaction is completed.

[0093] S3. To the product of S2, 16 parts of 1,6-hexanediol diacrylate, 7.5 parts of graphene-regulated nano silicon dioxide agent, 5.5 parts of magnesium oxide modifier, 17.5 parts of active diluent, 2 parts of silane coupling agent KH570, 2 parts of benzophenone photoinitiator, 2 parts of carbon black, 2 parts of polyethylene glycol 2000, and 4 parts of (ethoxyl) trimethylolpropane tri(methyl) acrylate EO-TMPTA are added and uniformly stirred, and finally UV ultraviolet irradiation curing is performed, and the light radiation energy is 2500 mJ / cm2.​2 , to obtain the modified urethane acrylate.

[0094] The preparation method of the graphene regulating nano-silica agent in the embodiment is as follows:

[0095] S01: heat treating the nano-silica at 220℃ for 12.5 min, then cooling to 67.5℃ at a rate of 2℃ / min, and obtaining the heat-treated nano-silica;

[0096] S02: mixing 4 parts of the heat-treated nano-silica, 1.5 parts of the lanthanum chloride solution, 3 parts of the sodium dodecyl benzene sulfonate solution, and 0.40 parts of the titanate coupling agent, and obtaining the nano-silica liquid;

[0097] S03: immersing the graphene in a sodium silicate solution with a concentration of 4 times that of the graphene for primary immersion treatment, then performing suction filtration and drying, immersing the graphene in a yttrium nitrate solution with a concentration of 3.5 times that of the graphene for secondary immersion treatment, and obtaining the graphene modifier after suction filtration and drying;

[0098] S04: ball milling the graphene modifier and the nano-silica liquid according to a weight ratio of 5:2, and obtaining the graphene regulating nano-silica agent after water washing and drying.

[0099] The mass fraction of the lanthanum chloride solution in the embodiment is 3.5%; and the mass fraction of the sodium dodecyl benzene sulfonate solution is 12.5%.

[0100] The pressure of the primary immersion treatment in the embodiment is 7.5 MPa, and the immersion time is 25 min; and the pressure of the secondary immersion treatment is 17.5 MPa, and the immersion time is 7.5 min.

[0101] The mass fraction of the sodium silicate solution in the embodiment is 6%; and the mass fraction of the yttrium nitrate solution is 3.5%.

[0102] The ball milling speed of the ball milling treatment in the embodiment is 1250 r / min, and the ball milling time is 1.5 h.

[0103] The preparation method of the magnesium oxide modifier in the embodiment is as follows:

[0104] S101: irradiating the magnesium oxide in a proton irradiation box for 12.5 min at an irradiation power of 320 W, and obtaining the irradiation agent after irradiation;

[0105] S102: adding 3.5 parts of the irradiation agent to 7.5 parts of a chitosan solution, then adding 1.5 parts of sodium lignosulfonate and 0.30 parts of a nano-silica sol, and performing ultrasonic treatment at an ultrasonic power of 230 W for 1.5 h, and obtaining the magnesium oxide modifier after ultrasonic treatment, water washing, and drying.

[0106] The mass fraction of the chitosan solution of the embodiment is 4%.

[0107] Comparative Example 1.

[0108] Different from Example 3 is that no graphene is added in the graphene-regulated nano-silica agent.

[0109] Comparative Example 2.

[0110] Different from Example 3 is that no graphene is added in the graphene-regulated nano-silica agent.

[0111] Comparative Example 3.

[0112] Different from Example 3 is that graphene is used instead of the graphene modifier.

[0113] Comparative Example 4.

[0114] Different from Example 3 is that the nano-silica liquid in the graphene-regulated nano-silica agent preparation is prepared by mixing nano-silica and deionized water in a weight ratio of 2:5.

[0115] Comparative Example 5.

[0116] Different from Example 3 is that no magnesium oxide modifier is added.

[0117] Comparative Example 6.

[0118] Different from Example 3 is that magnesium oxide is used instead of the magnesium oxide modifier.

[0119] The product performance of Examples 1-3 and Comparative Examples 1-6 of the application is tested, the impact toughness is tested according to GB / T 1732-2020 “Paint Film Impact Resistance Test Method”, the maximum value is 50 cm, and the wear resistance is tested according to the requirements of GB / T 23999-2009 standard test, which is ≤0.030 g.

[0120]

[0121] As can be seen from Examples 1-3 and Comparative Examples 1-6, the product of the application has excellent impact toughness and wear resistance, and the two performances can be improved in coordination. The combination of the graphene-regulated nano-silica agent and the magnesium oxide modifier has a significant advantage in improving the performance of the product. When no graphene modifier is added in the graphene-regulated nano-silica agent preparation, graphene is used instead of the graphene modifier, the nano-silica liquid is prepared by mixing nano-silica and deionized water in a weight ratio of 2:5, and magnesium oxide is used instead of the magnesium oxide modifier, the performance of the product is all deteriorated, and the wear resistance is more than ten times different. Only when the product is prepared by the method of the application, the performance of the product is the most significant.

[0122] It will be obvious to a person skilled in the art that the application is not limited to the details of the above-described exemplary embodiments, but that the application can be implemented in other embodiments without departing from the scope of the application. The embodiments are therefore to be seen as exemplary and in no way restrictive, the scope of the application being defined by the claims below rather than by the above description, and all variations falling within the meaning and range of equivalency of the essential characteristics of the claims are therefore intended to be embraced therein.

[0123] Furthermore, it should be understood that although the present specification describes exemplary embodiments, the application is not limited to only one independent technical solution in each embodiment, and the present specification is described in this way only for the sake of clarity, and a person skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that a person skilled in the art can understand.

Claims

1. A radiation-cured coating, characterized in that, The radiation-cured coating is a modified urethane acrylate; The specific modification method is as follows: S1.120-125 parts by weight of monoethanolamine are added to a 500 mL four-necked flask, protected by nitrogen gas, stirred continuously, heated to 40-50°C, and 175-177 parts by weight of ethylene carbonate are slowly added dropwise over half an hour. The mixture is kept at 50°C for 3-4 hours until all the monoethanolamine is consumed. The reaction formula is as follows. ； S2. Synthesis of urethane (meth)acrylate polyester: 1 mole of the product from step S1., 0.1 g of N,N-dinaphthyl-p-phenylenediamine, and 3 mL of 2.5% lithium hydroxide methanol solution were added to a 500 mL four-necked flask. A reflux condenser was installed, and 200-218 parts by weight of methyl methacrylate were added. The polymerization inhibitor hydroquinone monomethyl ether was added under continuous stirring, and the mixture was heated to 115-120 °C. The reaction was stirred continuously for 4 hours. The theoretical value of 98.3% of the methanol was collected and distilled off. S3. Add 10-20 parts of 1,6-hexanediol diacrylate, 5-10 parts of graphene-modified nano-silica agent, 4-7 parts of magnesium oxide modifier, 15-20 parts of reactive diluent, 1-3 parts of silane coupling agent KH570, 1-3 parts of benzophenone photoinitiator, 1-3 parts of carbon black, 1-3 parts of polyethylene glycol with a molecular weight less than 2500, and 3(ethoxy)trimethylolpropane tri(meth)acrylate 3EO-TMPTA to the product of S2. Stir and mix well, and finally cure by UV irradiation with a light radiation energy of 2000-3000 mJ / cm². 2 Modified urethane acrylate can then be obtained; The preparation method of the graphene-modified nano-silica agent is as follows: S01: Heat-treat nano-silica at 210-230℃ for 10-15 min, then cool it to 65-70℃ at a rate of 1-3℃ / min and keep it at the temperature to obtain heat-insulated nano-silica. S02: Mix 3-5 parts of heat-insulating nano-silica, 1-2 parts of lanthanum chloride solution, 2-4 parts of sodium dodecylbenzenesulfonate solution and 0.35-0.55 parts of titanate coupling agent, stir and mix well to obtain nano-silica liquid; S03: First immersion treatment: immerse graphene in a sodium silicate solution of 3-5 times the volume of graphene, then filter and dry, then immerse it in a yttrium nitrate solution of 2-5 times the volume of graphene for second immersion treatment. After immersion, filter and dry to obtain graphene modifier. S04: Graphene modifier and nano silica liquid are ball-milled at a weight ratio of 5:

2. After ball milling, the mixture is washed with water and dried to obtain graphene-modified nano silica agent. The preparation method of the magnesium oxide modifier is as follows: S101: Place magnesium oxide in a proton irradiation chamber and irradiate for 10-15 minutes at an irradiation power of 300-350W. After irradiation, the irradiant is obtained. S102: Add 2-5 parts of irradiant to 5-10 parts of chitosan solution, then add 1-2 parts of sodium lignosulfonate and 0.35-0.55 parts of nano silica sol, and sonicate at an ultrasonic power of 220-240W for 1-2 hours. After sonication, wash with water and dry to obtain magnesium oxide modifier.

2. The radiation-cured coating according to claim 1, characterized in that, The lanthanum chloride solution has a mass fraction of 2-5%; the sodium dodecylbenzenesulfonate solution has a mass fraction of 10-15%.

3. The radiation-cured coating according to claim 1, characterized in that, The pressure of the first-stage immersion treatment is 5-10 MPa, and the immersion time is 20-30 min; the pressure of the second-stage immersion treatment is 15-20 MPa, and the immersion time is 5-10 min.

4. The radiation-cured coating according to claim 1, characterized in that, The sodium silicate solution has a mass fraction of 4-8%; The mass fraction of the yttrium nitrate solution is 2-5%.

5. The radiation-cured coating according to claim 1, characterized in that, The ball milling process is carried out at a speed of 1000-1500 r / min for 1-2 hours.

6. The radiation-cured coating according to claim 1, characterized in that, The chitosan solution has a mass fraction of 3-5%.

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