A putty based on ultraviolet light-cured resin and a preparation method and application thereof

Abstract

The application belongs to the technical field of coatings, and particularly relates to a putty based on ultraviolet light curing resin and a preparation method and application thereof. The putty based on ultraviolet light curing resin comprises, by mass fraction, 30-50 parts of ultraviolet light curing resin, 25-45 parts of fillers, 3-6 parts of diluents, 3-6 parts of poly(methyl methacrylate-co-methyl methacrylate), and 0.05-1.5 parts of a photoinitiator. The ultraviolet light curing resin comprises a light curing unsaturated polyester resin and a polyester acrylate. The fillers comprise antioxidants / halloysite nanotubes / basalt fibers, nano calcium carbonate, and nano zirconium oxide. The putty based on ultraviolet light curing resin has good adhesion, flexibility, impact resistance, heat resistance, and high and low temperature resistance, and can be applied in the fields of automobile repair and furniture manufacturing.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to an atomic putty based on ultraviolet light curing resin, its preparation method, and its application. Background Technology

[0002] Putty is used to fill and repair defects such as pits, welds, cracks, and pinholes in substrates, and is widely used in the automotive, furniture, train, high-speed rail, and shipbuilding industries. Traditional putty, also known as unsaturated polyester resin putty, mainly consists of components A and B. Component A comprises unsaturated polyester resin, styrene, pigments, fillers, accelerators, toughening agents, and polymerization inhibitors, while component B is the curing agent, primarily composed of organic peroxides (cyclohexanone peroxide or methyl ethyl ketone peroxide). However, it requires fresh preparation and has a long curing time, and styrene has a certain degree of toxicity, raising safety concerns.

[0003] To address the aforementioned technical issues, Chinese Patent CN113150597A discloses a non-light-curing flash-drying sheet metal putty and its preparation method. This non-light-curing flash-drying sheet metal putty comprises, by weight, the following raw materials: 17%–30% light-curing component, 9%–15% monomer, 61%–80% talc, 0.2%–1% fumed silica, and 0.5%–1% dispersant. The putty contains light-curing resin and photoinitiator, and after application, it only requires two seconds of illumination to fully cure, achieving non-light-curing flash-drying performance. The main raw materials are light-curing resin, talc, and barium sulfate, and the raw materials are solvent-free, achieving zero VOC emissions. However, this technical solution does not disclose the specific composition and effects of the light-curing resin, limiting its application prospects.

[0004] Chinese Patent Publication No. CN107858080A discloses a UV repair coating, which is manufactured by mixing the following components in the indicated mass percentages: 10-99.1% of a compound containing olefinic unsaturated double bonds; 0.5-50% of a diluent; 0.01-10% of a free radical polymerization initiator; and 0-80% of an auxiliary agent. The compound containing olefinic unsaturated double bonds is selected from one or more of unsaturated polyesters, epoxy acrylic resins, polyurethane acrylic resins, polyether acrylic resins, polyester acrylic resins, and their modified forms or derivatives. This coating differs from traditional UV coatings and can be used to repair damaged surfaces such as walls or floors. However, the relatively low filler content in this technical solution may result in suboptimal repair effects. Summary of the Invention

[0005] To address the above-mentioned problems, this invention provides an atomic putty based on ultraviolet light-curing resin, its preparation method, and its application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] The first aspect of this invention provides an atomic putty based on ultraviolet-curable resin, wherein the raw materials, by weight, include: 30-50 parts of ultraviolet-curable resin, 25-45 parts of filler, 3-6 parts of diluent, 3-6 parts of poly(methyl methacrylate-co-methacrylic acid), and 0.05-1.5 parts of photoinitiator;

[0008] The UV-curable resin comprises UV-curable unsaturated polyester resin and polyester acrylate; the mass ratio of the UV-curable unsaturated polyester to polyester acrylate is (6-10):(2-4), preferably 8:3;

[0009] The filler comprises antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia; the mass ratio of antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia is (15-20):(2-6):1, preferably 18:4:1.

[0010] Preferably, the polyester acrylate has a functionality of 2 and is purchased from Kunshan Castel Polymer Materials Co., Ltd., model U-Cure 9215.

[0011] Preferably, the poly(methyl methacrylate-co-methacrylic acid) has a weight-average molecular weight of 3400 and is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number: P478276.

[0012] Preferably, the mass ratio of the UV-curable resin, filler and poly(methyl methacrylate-co-methacrylic acid) is (8-10):(7-10):1, and more preferably 10:9:1.

[0013] Preferably, the method for preparing the photocurable unsaturated polyester resin includes the following steps:

[0014] S1. Under nitrogen protection, a dicarboxylic acid, phthalic anhydride and a diol undergo a polycondensation reaction in the presence of dibutyltin dilaurate to obtain an esterified product.

[0015] S2. Polycaprolactone diol is added to the esterified product in step S1 to continue the polycondensation reaction and obtain saturated polyester resin.

[0016] S3. Mix saturated polyester resin and butyl acetate evenly, add ethyl isocyanate acrylate to react, and obtain light-cured unsaturated polyester resin.

[0017] To address the issues of traditional two-component putty requiring on-the-spot preparation and long curing times, this invention introduces unsaturated double bonds into the polyester resin by reacting the isocyanate groups in ethyl isocyanate acrylate with saturated polyester resin. This allows the unsaturated polyester resin to be cured under ultraviolet light. Furthermore, the inventors have discovered that the resulting putty exhibits excellent adhesion and flexibility, which they speculate is due to the formation of urethane bonds, which allows for a stronger chemical bond with the substrate. Additionally, the introduction of flexible segments increases the free volume between molecules.

[0018] However, the inventors discovered that the heat resistance of the putty was poor, which they speculated was due to the presence of thermally weak urethane bonds and unsaturated bonds. To solve this technical problem, the inventors unexpectedly discovered that when UV-cured unsaturated polyester resin and polyester acrylate were compounded, and poly(methyl methacrylate-co-methacrylic acid) was added, the resulting putty not only had excellent heat resistance, but also significantly improved the adhesion, flexibility and impact resistance of the putty. However, the inventors also found that the mass ratio of UV-cured resin, filler and poly(methyl methacrylate-co-methacrylic acid) needed to be controlled at (8-10):(7-10):1, otherwise the performance of the putty would decrease.

[0019] Preferably, the dicarboxylic acid in step S1 is a mixture of 1,4-cyclohexanedicarboxylic acid and succinic acid; and the diol is a mixture of 2-methyl-2-ethyl-1,3-propanediol and dipropylene glycol.

[0020] More preferably, the mass ratio of 1,4-cyclohexanedicarboxylic acid, succinic acid, phthalic anhydride, 2-methyl-2-ethyl-1,3-propanediol, dipropylene glycol and dibutyltin dilaurate is (2-5):(2-4):(1-2):(4-7):(1-3):(0.2-0.7).

[0021] More preferably, the mass ratio of 1,4-cyclohexanedicarboxylic acid, succinic acid, phthalic anhydride, 2-methyl-2-ethyl-1,3-propanediol, dipropylene glycol, and dibutyltin dilaurate is 4:3:1.8:6:

[0022] 2.5:0.6.

[0023] Preferably, the temperature of the polycondensation reaction in step S1 is 180-200℃, and the reaction time is 3-6 hours.

[0024] More preferably, the temperature of the polycondensation reaction in step S1 is 200°C, and the reaction time is 5 hours.

[0025] Preferably, the mass ratio of the esterified product to polycaprolactone diol in step S2 is 10:(1-3), more preferably 10:2.

[0026] Preferably, the number average molecular weight of the polycaprolactone diol is 1000-3000, and more preferably 2000.

[0027] Preferably, the temperature of the polycondensation reaction in step S2 is 240-270°C, and the reaction time is 2-4 hours.

[0028] More preferably, the temperature of the polycondensation reaction in step S2 is 260°C, and the reaction time is 3 hours.

[0029] Preferably, the mass ratio of the saturated polyester resin, butyl acetate and ethyl isocyanate acrylate in step S3 is 1:(1-1.5):(0.02-0.05), and more preferably 1:1.2:0.03.

[0030] Preferably, the reaction temperature in step S3 is 50-70°C, and the reaction time is 2-6 hours.

[0031] More preferably, the reaction temperature in step S3 is 60°C, and the reaction time is 4 hours.

[0032] Preferably, the particle size of the nano-calcium carbonate is 20-40 nm, and more preferably 20 nm.

[0033] Preferably, the preparation method of the antioxidant / haloysite nanotube / basalt fiber includes the following steps:

[0034] Step 1: Completely immerse the basalt fiber in concentrated nitric acid for acidification, wash until neutral, and dry to obtain acidified basalt fiber;

[0035] Step 2: Mix the acidified basalt fiber, dopamine hydrochloride, γ-methacryloxypropyltrimethoxysilane alcohol solution and alkaline solvent 1 evenly, stir and react, and after the reaction is completed, wash and dry to obtain modified basalt fiber.

[0036] Step 3: Mix halloysite nanotubes and γ-mercaptopropyltrimethoxysilane solution evenly, stir and react. After the reaction is complete, wash and dry to obtain modified halloysite nanotubes.

[0037] Step 4: Disperse the antioxidant in ethanol, add the modified halloysite nanotubes, sonicate, and apply vacuum negative pressure to obtain halloysite nanotubes loaded with antioxidants.

[0038] Step 5: Mix the modified basalt fiber, halloysite carbon nanotubes loaded with antioxidants, and alkaline solvent 2, stir and react. After the reaction is complete, wash and dry to obtain antioxidant / haloysite nanotubes / basalt fiber.

[0039] In cold regions, large diurnal temperature variations cause putty to crack and detach easily when subjected to sudden temperature changes. To address this problem, the inventors have creatively prepared an antioxidant / haloysite nanotube / basalt fiber composite. Carbon-carbon double bonds are introduced into the basalt fiber, and thiol groups are introduced into the halloysite nanotube. Simultaneously, the antioxidant is loaded into the halloysite nanotube. Through the reaction of the carbon-carbon double bonds and thiol groups, a composite of basalt fiber and halloysite nanotube is formed. Theoretically, during curing, the antioxidant / haloysite nanotube / basalt fiber composite can be freely bent and interwoven, forming a supporting structure. This not only improves the flexibility of the putty but also… It can also buffer temperature changes, reduce shrinkage, and reduce stress damage caused by cold expansion and thermal contraction. However, the inventors found that if only antioxidants / haloysite nanotubes / basalt fibers are used as fillers, the adhesion of the putty is low, and the high and low temperature resistance cannot reach 30 cycles. It is speculated that this is because only antioxidants / haloysite nanotubes / basalt fibers can not fully fill the tiny pores of the resin matrix. To solve this technical problem, the inventors unexpectedly discovered that when the filler includes antioxidants / haloysite nanotubes / basalt fibers, nano calcium carbonate, and nano zirconium oxide, the putty obtained has excellent adhesion, flexibility, impact resistance, and high and low temperature cycle resistance.

[0040] Preferably, the basalt fibers in step S1 are granular with an average fiber length of 3-6 mm.

[0041] Preferably, the acidification temperature in step 1 is 55-65℃, and the acidification time is 2-4h.

[0042] More preferably, the acidification temperature in step 1 is 60°C, and the acidification time is 3 hours.

[0043] Preferably, the mass ratio of the acidified basalt fiber, dopamine hydrochloride, γ-methacryloxypropyltrimethoxysilane and alkaline solvent 1 in step 2 is (5-10):(0.1-0.3):(3-8):100, more preferably 8:0.2:6:100.

[0044] Preferably, the alcoholic solution of γ-methacryloxypropyltrimethoxysilane in step 2 is composed of γ-methacryloxypropyltrimethoxysilane and ethanol in a mass ratio of (1-3):100.

[0045] Preferably, the alkaline solvent 1 in step 2 is a Tris-HCl buffer solution with a pH of 9-10.

[0046] Preferably, the temperature of the stirring reaction in step 2 is 40-50℃, the stirring speed is 300-600 rpm, and the stirring time is 8-12 h.

[0047] Preferably, in step 3, the mass ratio of halloysite nanotubes to γ-mercaptopropyltrimethoxysilane solution is 1:(30-50), more preferably 1:40.

[0048] Preferably, the γ-mercaptopropyltrimethoxysilane solution in step 3 is composed of γ-mercaptopropyltrimethoxysilane and ethanol in a mass ratio of 0.05-0.1:100.

[0049] Preferably, the stirring speed in step 3 is 200-400 rpm, and the stirring time is 30-60 min.

[0050] More preferably, the stirring speed in step 3 is 300 rpm, and the stirring time is 40 min.

[0051] Preferably, the antioxidant in step 4 is a mixture of tea polyphenols and 3,3'-thiodipropionic acid.

[0052] More preferably, the mass ratio of the tea polyphenols, 3,3'-thiodipropionic acid, ethanol and modified halloysite nanotubes is (1-3):(0.5-1.5):100:(2-5), and more preferably 1.5:1:100:3.

[0053] Preferably, the ultrasound time in step 4 is 30-60 minutes, and the vacuum negative pressure time is 30-60 minutes.

[0054] More preferably, the ultrasound time in step 4 is 40 minutes, and the vacuum negative pressure time is 40 minutes.

[0055] Preferably, the mass ratio of the modified basalt fiber, the halloysite carbon nanotube loaded with antioxidant, and the alkaline solvent 2 in step 5 is 1:(2-4):100.

[0056] Preferably, the alkaline solvent 2 in step 5 is a phosphate buffer solution with a phosphate concentration of 10 mM and a pH of 7.2-7.4.

[0057] Preferably, the temperature of the stirring reaction in step 5 is 25°C, the stirring speed is 50-100 rpm, and the stirring time is 7-10 h.

[0058] More preferably, the temperature of the stirring reaction in step 5 is 25°C, the stirring speed is 80 rpm, and the stirring time is 9 hours.

[0059] Preferably, the diluent is selected from at least one of dipropylene glycol diacrylate, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane triacrylate, and is preferably dipropylene glycol diacrylate.

[0060] Preferably, the photoinitiator is selected from at least one of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin diethyl ether, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0061] Preferably, the photoinitiator is a mixture of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzoin diethyl ether; the mass ratio of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzoin diethyl ether is (3-5):(1-3):(2-6).

[0062] More preferably, the mass ratio of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin diethyl ether is 4:2:4.

[0063] The second aspect of the present invention provides a method for preparing the above-mentioned putty based on ultraviolet curable resin, comprising the following steps: mixing ultraviolet curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid) and photoinitiator evenly to obtain the putty.

[0064] The third aspect of this invention provides the application of the above-mentioned putty based on ultraviolet light curing resin in the fields of automotive repair, furniture manufacturing, and decoration.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] 1. This invention introduces unsaturated double bonds into polyester resin by reacting the isocyanate groups in ethyl isocyanate acrylate with saturated polyester resin, thereby enabling the unsaturated polyester resin to be cured by ultraviolet light, and the resulting putty has good adhesion and flexibility.

[0067] 2. This invention uses a combination of UV-curable unsaturated polyester resin and polyester acrylate, and adds poly(methyl methacrylate-co-methacrylic acid). The mass ratio of UV-curable resin, filler and poly(methyl methacrylate-co-methacrylic acid) is controlled to be (8-10):(7-10):1. The resulting putty not only has excellent heat resistance, but also significantly improves the adhesion, flexibility and impact resistance of the putty.

[0068] 3. When the filler of this invention includes antioxidants / haloysite nanotubes / basalt fibers, nano-calcium carbonate, and nano-zirconia, the resulting atomic putty has excellent adhesion, flexibility, impact resistance, and resistance to high and low temperature cycling. Detailed Implementation

[0069] To provide a clearer understanding of the technical features, objectives, and effects of this invention, specific implementation schemes are now described in detail.

[0070] The present invention will be further described below with reference to embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0071] Unless otherwise specified, all raw materials used in the following examples and comparative examples are commercially available or prepared by conventional methods in the art.

[0072] Example 1

[0073] A type of putty based on ultraviolet-curable resin, by weight, consists of 30 parts ultraviolet-curable resin, 25 parts filler, 3 parts diluent, 3 parts poly(methyl methacrylate-co-methacrylic acid), and 0.05 parts photoinitiator.

[0074] The weight-average molecular weight of poly(methyl methacrylate-co-methacrylic acid) was 3400. It was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number: P478276.

[0075] The UV-curable resin comprises UV-curable unsaturated polyester resin and polyester acrylate; the mass ratio of the UV-curable unsaturated polyester to polyester acrylate is 8:3.

[0076] The polyester acrylate has a functionality of 2 and was purchased from Kunshan Castel Polymer Materials Co., Ltd., model number U-Cure 9215.

[0077] The method for preparing the photocurable unsaturated polyester resin is as follows:

[0078] S1. Under nitrogen protection, a dicarboxylic acid, phthalic anhydride and a diol undergo a polycondensation reaction in the presence of dibutyltin dilaurate to obtain an esterified product.

[0079] S2. Polycaprolactone diol is added to the esterified product in step S1 to continue the polycondensation reaction and obtain saturated polyester resin.

[0080] S3. Mix saturated polyester resin and butyl acetate evenly, add ethyl isocyanate acrylate to react, and obtain light-cured unsaturated polyester resin.

[0081] The dicarboxylic acid mentioned in step S1 is a mixture of 1,4-cyclohexanedicarboxylic acid (CAS No.: 1076-97-7) and succinic acid (CAS No.: 110-15-6); the diol is a mixture of 2-methyl-2-ethyl-1,3-propanediol (CAS No.: 77-84-9) and dipropylene glycol (CAS No.: 25265-71-8).

[0082] The mass ratio of 1,4-cyclohexanedicarboxylic acid, succinic acid, phthalic anhydride (CAS No.: 85-44-9), 2-methyl-2-ethyl-1,3-propanediol, dipropylene glycol, and dibutyltin dilaurate (CAS No.: 77-58-7) is 4:3:1.8:6:2.5:0.6.

[0083] The polycondensation reaction in step S1 is carried out at a temperature of 200°C for 5 hours.

[0084] The mass ratio of the esterified product to polycaprolactone diol in step S2 is 10:2.

[0085] The polycaprolactone diol has a number average molecular weight of 2000 and was purchased from Xuzhou Yihuiyang New Material Co., Ltd., model: PCL-2000.

[0086] The polycondensation reaction in step S2 is carried out at a temperature of 260°C for 3 hours.

[0087] The mass ratio of the saturated polyester resin, butyl acetate (CAS No.: 123-86-4), and ethyl isocyanate acrylate (CAS No.: 13641-96-8) in step S3 is 1:1.2:0.03.

[0088] The reaction temperature in step S3 is 60°C, and the reaction time is 4 hours.

[0089] The filler comprises antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia; the mass ratio of antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia is 18:4:1.

[0090] The nano-calcium carbonate has a particle size of 20 nm and was purchased from Ningbo Luofei Nanotechnology Co., Ltd., product number: LF-CaCO3-N20.

[0091] The nano-zirconia was purchased from Langfang Nake New Material Technology Co., Ltd., model number: ZO-P-3Y.

[0092] The preparation method of the antioxidant / haloysite nanotube / basalt fiber is as follows:

[0093] Step 1: Completely immerse the basalt fiber in concentrated nitric acid (98% concentrated nitric acid) for acidification, wash until neutral, and dry to obtain acidified basalt fiber;

[0094] Step 2: Mix the acidified basalt fiber, dopamine hydrochloride, γ-methacryloxypropyltrimethoxysilane alcohol solution and alkaline solvent 1 evenly, stir and react, and after the reaction is completed, wash and dry to obtain modified basalt fiber.

[0095] Step 3: Mix halloysite nanotubes and γ-mercaptopropyltrimethoxysilane solution evenly, stir and react. After the reaction is complete, wash and dry to obtain modified halloysite nanotubes.

[0096] Step 4: Disperse the antioxidant in ethanol, add the modified halloysite nanotubes, sonicate, and apply vacuum negative pressure to obtain halloysite nanotubes loaded with antioxidants.

[0097] Step 5: Mix the modified basalt fiber, halloysite carbon nanotubes loaded with antioxidants, and alkaline solvent 2, stir and react. After the reaction is complete, wash and dry to obtain antioxidant / haloysite nanotubes / basalt fiber.

[0098] The basalt fibers mentioned in step 1 are granular, with an average fiber length of 3-6 mm, and were purchased from Changsha North America Fu New Material Technology Co., Ltd., model: 1000.

[0099] The acidification temperature in step 1 is 60°C, and the acidification time is 3 hours.

[0100] The mass ratio of acidified basalt fiber, dopamine hydrochloride (CAS No.: 62-31-7), γ-methacryloyloxypropyltrimethoxysilane (CAS No.: 2530-85-0), and alkaline solvent 1 in step 2 is 8:0.2:6:100.

[0101] The alcoholic solution of γ-methacryloxypropyltrimethoxysilane in step 2 is composed of γ-methacryloxypropyltrimethoxysilane and ethanol in a mass ratio of 2:100.

[0102] The alkaline solvent 1 in step 2 is a Tris-HCl buffer solution, 1M, pH 9, purchased from Wuhan AmyJet Technology Co., Ltd., product number MBS545577.

[0103] The temperature of the stirring reaction in step 2 is 45℃, the stirring speed is 500 rpm, and the stirring time is 10 h.

[0104] In step 3, the mass ratio of halloysite nanotubes to γ-mercaptopropyltrimethoxysilane solution is 1:40.

[0105] Halloysite nanotubes were purchased from Guangdong Jina New Materials Technology Co., Ltd., model: JN-3 halloysite.

[0106] The γ-mercaptopropyltrimethoxysilane solution in step 3 is composed of γ-mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0) and ethanol in a mass ratio of 0.1:100.

[0107] The stirring speed in step 3 is 300 rpm, and the stirring time is 40 min.

[0108] The antioxidant mentioned in step 4 is a mixture of tea polyphenols and 3,3'-thiodipropionic acid (CAS No.: 111-17-1).

[0109] The mass ratio of tea polyphenols, 3,3'-thiodipropionic acid, ethanol and modified halloysite nanotubes is 1.5:1:100:3.

[0110] The ultrasound time in step 4 is 40 minutes, and the vacuum negative pressure time is 40 minutes.

[0111] In step 5, the mass ratio of the modified basalt fiber, the halloysite carbon nanotubes loaded with antioxidants, and the alkaline solvent 2 is 1:3:100.

[0112] The alkaline solvent 2 mentioned in step 5 is a phosphate buffer solution with a phosphate concentration of 10 mM and a pH of 7.2-7.4. It was purchased from Wuhan Pronosai Life Technology Co., Ltd., product number: PB180327.

[0113] The stirring reaction in step 5 is carried out at a temperature of 25°C, a stirring speed of 80 rpm, and a stirring reaction time of 9 hours.

[0114] The diluent is dipropylene glycol diacrylate (CAS: 57472-68-1).

[0115] The photoinitiator is a mixture of 1-hydroxycyclohexylbenzophenone (CAS No.: 947-19-3), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (CAS No.: 75980-60-8), and benzoin diethyl ether (CAS No.: 24650-42-8); the mass ratio of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin diethyl ether is 4:2:4.

[0116] The above-mentioned method for preparing putty based on UV-curable resin is as follows: UV-curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid) and photoinitiator are mixed evenly to obtain the putty.

[0117] Example 2

[0118] The difference from Example 1 is that the putty based on UV-curable resin, by weight, consists of 50 parts UV-curable resin, 45 parts filler, 6 parts diluent, 6 parts poly(methyl methacrylate-co-methacrylic acid), and 1.5 parts photoinitiator; the rest are the same.

[0119] The preparation method of the above-mentioned putty based on UV-curable resin is the same as in Example 1.

[0120] Example 3

[0121] The difference from Example 1 is that the putty based on UV-curable resin, by mass, consists of 40 parts UV-curable resin, 36 parts filler, 5 parts diluent, 4 parts poly(methyl methacrylate-co-methacrylic acid), and 1 part photoinitiator; all other components are the same.

[0122] The preparation method of the above-mentioned putty based on UV-curable resin is the same as in Example 1.

[0123] Comparative Example 1

[0124] The difference from Example 3 is that the polyester acrylate is replaced with an equal mass of light-cured unsaturated polyester resin; all other aspects are the same.

[0125] Comparative Example 2

[0126] The difference from Example 3 is that poly(methyl methacrylate-co-methacrylic acid) is replaced with an equal mass of polyester acrylate; otherwise, they are the same.

[0127] Comparative Example 3

[0128] The difference from Example 3 is that poly(methyl methacrylate-co-methacrylic acid) was replaced with an equal mass of polymethyl methacrylate (CAS No.: 9011-14-7); all other aspects are the same.

[0129] Comparative Example 4

[0130] The difference from Example 3 is that the filler is an antioxidant / haloite nanotube / basalt fiber; otherwise, they are the same.

[0131] Comparative Example 5

[0132] The difference from Example 3 is that nano-zirconia is replaced with an equal mass of nano-calcium carbonate; otherwise, they are the same.

[0133] Comparative Example 6

[0134] The difference from Example 3 is that the antioxidant / haloysite nanotubes / basalt fibers are replaced with an equal mass of halloysite nanotubes loaded with antioxidant; otherwise, they are the same.

[0135] Comparative Example 7

[0136] The difference from Example 3 is that the preparation method of the antioxidant / haloysite nanotube / basalt fiber is as follows: Steps 1-4 are the same as in Example 3; Step 5, the modified basalt fiber and the halloysite carbon nanotube loaded with antioxidant are mixed to obtain the product; the mass ratio of the modified basalt fiber to the halloysite carbon nanotube loaded with antioxidant is 1:3; the rest are the same.

[0137] Comparative Example 8

[0138] The difference from Example 3 is that the putty based on UV-curable resin, by weight, consists of 30 parts UV-curable resin, 41 parts filler, 5.5 parts diluent, 9 parts poly(methyl methacrylate-co-methacrylic acid), and 0.5 parts photoinitiator; the rest are the same.

[0139] Performance testing:

[0140] The repair materials prepared by applying the putty based on UV-curable resin of Examples 1-3 and Comparative Examples 1-8 to galvanized steel sheets were respectively coated with a thickness of 0.5 mm and cured at an energy of 1500 mJ / cm². 2 Crosslinking curing was performed under UV curing conditions for 3 seconds. After curing, the galvanized sheet was placed in a dry and ventilated place and dried for 24 hours before the following tests were conducted:

[0141] 1. Adhesion: Test standard: GB / T5210-2006;

[0142] 2. Flexibility: Test standard: GB / T 1731-2020, the minimum shaft diameters used are 15mm, 25mm, 50mm and 100mm respectively;

[0143] 3. Impact resistance: Test standard: GB / T1732-2020, the height is adjusted in multiples of 5cm each time;

[0144] 4. Heat resistance: Place at 160℃ for 10 hours, cool to room temperature, and observe the coating film. If the coating film is undamaged, it is considered qualified; otherwise, it is unqualified.

[0145] 5. Resistance to high and low temperatures: Placed at 60℃ for 8 hours, then removed and placed at room temperature for 2 hours, then placed at -60℃ for 8 hours, then removed and placed at room temperature for 2 hours, this is counted as one cycle. If no cracking or peeling occurs after 30 cycles, it is considered qualified; otherwise, it is unqualified.

[0146] The results are shown in Table 1:

[0147] Table 1. Performance test results of putty based on UV-curable resin in Examples 1-3 and Comparative Examples 1-8.

[0148]

[0149] As can be seen from Table 1, the putty based on UV-curable resin in Examples 1-3 has good adhesion, flexibility, impact resistance, heat resistance and high and low temperature resistance.

[0150] In Comparative Example 1, when polyester acrylate was replaced with an equal mass of light-cured unsaturated resin, the resulting putty exhibited decreased adhesion, flexibility, and impact resistance, and failed to meet heat resistance standards.

[0151] In Comparative Example 2, when poly(methyl methacrylate-co-methacrylic acid) was replaced with an equal mass of polyester acrylate, the resulting putty exhibited decreased flexibility, decreased impact resistance, and failed to meet heat resistance standards.

[0152] In Comparative Example 3, when poly(methyl methacrylate-co-methacrylic acid) was replaced with an equal mass of polymethyl methacrylate, the adhesion and impact resistance of the resulting putty decreased, but the flexibility was severely reduced, and the high and low temperature resistance was unqualified.

[0153] Comparative Example 4 filler contained only antioxidant / haloite nanotubes / basalt fibers, resulting in a low adhesion of the resulting putty, as well as reduced flexibility and impact resistance, and unsatisfactory high and low temperature resistance.

[0154] Comparative Example 5: When nano-zirconia was replaced with an equal mass of nano-calcium carbonate, the resulting putty exhibited decreased adhesion, flexibility, and impact resistance, and failed to meet the high and low temperature resistance standards.

[0155] Comparative Example 6 replaced the antioxidant / haloysite nanotubes / basalt fibers with the same mass of halloysite nanotubes loaded with antioxidants. The resulting putty showed decreased adhesion, reduced impact resistance, significantly reduced flexibility, and failed to meet the requirements for heat resistance and high and low temperature resistance.

[0156] Comparative Example 7 directly mixed modified basalt fiber and halloysite carbon nanotubes loaded with antioxidants. The resulting putty had reduced adhesion, flexibility, and impact resistance, and failed to meet the high and low temperature resistance requirements.

[0157] In Comparative Example 8, the mass ratio of UV-curable resin, filler, and poly(methyl methacrylate-co-methyl methacrylate) was not within the range of (8-10):(7-10):1. As a result, the adhesion, flexibility, and impact resistance of the resulting putty were significantly reduced, and its high and low temperature resistance was unqualified.

[0158] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A putty based on ultraviolet-curable resin, characterized in that, By weight, the raw materials include: 30-50 parts UV-curable resin, 25-45 parts filler, 3-6 parts diluent, 3-6 parts poly(methyl methacrylate-co-methacrylic acid), and 0.05-1.5 parts photoinitiator; The UV-curable resin comprises UV-curable unsaturated polyester resin and polyester acrylate; the mass ratio of the UV-curable unsaturated polyester to polyester acrylate is (6-10):(2-4). The filler comprises antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia; the mass ratio of antioxidant / haloysite nanotubes / basalt fiber, nano-calcium carbonate, and nano-zirconia is (15-20):(2-6):

1.

2. The putty based on UV-curable resin according to claim 1, characterized in that, The mass ratio of the UV-curable resin, filler, and poly(methyl methacrylate-co-methyl methacrylate) is (8-10):(7-10):

1.

3. The putty based on UV-curable resin according to claim 2, characterized in that, The method for preparing the photocurable unsaturated polyester resin includes the following steps: S1. Under nitrogen protection, a dicarboxylic acid, phthalic anhydride and a diol undergo a polycondensation reaction in the presence of dibutyltin dilaurate to obtain an esterified product. S2. Polycaprolactone diol is added to the esterified product in step S1 to continue the polycondensation reaction and obtain saturated polyester resin. S3. Mix saturated polyester resin and butyl acetate evenly, add ethyl isocyanate acrylate to react, and obtain light-cured unsaturated polyester resin.

4. The putty based on UV-curable resin according to claim 3, characterized in that, The dicarboxylic acid mentioned in step S1 is a mixture of 1,4-cyclohexanedicarboxylic acid and succinic acid; the diol is a mixture of 2-methyl-2-ethyl-1,3-propanediol and dipropylene glycol.

5. The putty based on UV-curable resin according to claim 1, characterized in that, The preparation method of the antioxidant / haloysite nanotube / basalt fiber includes the following steps: Step 1: Completely immerse the basalt fiber in concentrated nitric acid for acidification, wash until neutral, and dry to obtain acidified basalt fiber; Step 2: Mix the acidified basalt fiber, dopamine hydrochloride, γ-methacryloxypropyltrimethoxysilane alcohol solution and alkaline solvent 1 evenly, stir and react, and after the reaction is completed, wash and dry to obtain modified basalt fiber. Step 3: Mix halloysite nanotubes and γ-mercaptopropyltrimethoxysilane solution evenly, stir and react. After the reaction is complete, wash and dry to obtain modified halloysite nanotubes. Step 4: Disperse the antioxidant in ethanol, add the modified halloysite nanotubes, sonicate, and apply vacuum negative pressure to obtain halloysite nanotubes loaded with antioxidants. Step 5: Mix the modified basalt fiber, halloysite nanotubes loaded with antioxidants, and alkaline solvent 2, stir and react. After the reaction is complete, wash and dry to obtain antioxidant / haloysite nanotubes / basalt fiber.

6. The putty based on UV-curable resin according to claim 5, characterized in that, The antioxidant mentioned in step 4 is a mixture of tea polyphenols and 3,3'-thiodipropionic acid tea polyphenols, wherein the mass ratio of tea polyphenols, 3,3'-thiodipropionic acid tea polyphenols and ethanol is (1-3):(0.5-1.5):

100.

7. The putty based on UV-curable resin according to any one of claims 1-6, characterized in that, The photoinitiator is selected from at least one of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, benzoin diethyl ether, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

8. The putty based on UV-curable resin according to claim 7, characterized in that, The photoinitiator is a mixture of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzoin diethyl ether; the mass ratio of 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzoin diethyl ether is (3-5):(1-3):(2-6).

9. The method for preparing putty based on ultraviolet-curable resin according to any one of claims 1-8, characterized in that, Includes the following steps: The UV-curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid), and photoinitiator are mixed evenly to obtain the final product.

10. The application of the putty based on UV-curable resin according to any one of claims 1-8 in the fields of automotive repair and furniture manufacturing.

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