Ultraviolet curing resin-based putty as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coatings, and particularly relates to putty based on ultraviolet curing resin as well as a preparation method and application of the putty. The putty based on the ultraviolet curing resin is prepared from the following raw materials in parts by mass: 30 to 50 parts of ultraviolet curing resin, 25 to 45 parts of filler, 3 to 6 parts of diluent, 3 to 6 parts of poly (methyl methacrylate-co-methacrylic acid) and 0.05 to 1.5 parts of photoinitiator, the ultraviolet light curing resin comprises light curing unsaturated polyester resin and polyester acrylate; the filler is prepared from an antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate and nano zirconium oxide; the putty based on the ultraviolet curing resin provided by the invention has good adhesive force, flexibility, impact resistance, heat resistance and high and low temperature resistance; the method can be applied to the fields of automobile repairing and furniture manufacturing.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and particularly relates to an atomic putty based on ultraviolet curable resin, a preparation method thereof and an application thereof. Background Art

[0002] Atomic putty is used for filling and modifying defects such as pits, welds, cracks, and pinholes on the substrate, and is widely used in fields such as automobiles, furniture, trains, high-speed rails, and ships. Traditional atomic putty, also known as unsaturated polyester resin putty, mainly consists of components A and B. Component A is composed of unsaturated polyester resin, styrene, pigments and fillers, accelerator, toughening agent, inhibitor, etc., and component B is a curing agent, and its main component is organic peroxide (cyclohexanone peroxide or methyl ethyl ketone peroxide). However, during use, it needs to be prepared and used immediately, and has the problem of long curing time, and styrene has certain toxicity and poor safety.

[0003] To solve the above technical problems, Chinese Patent with publication number CN113150597A discloses a matte-curing flash-drying sheet metal atomic putty and a preparation method thereof. The matte-curing flash-drying sheet metal atomic putty includes the following raw materials in parts by weight: 17% - 30% of a photocuring component, 9% - 15% of a monomer, 61% - 80% of a talc material, 0.2% - 1% of fumed silica, and 0.5% - 1% of a dispersant; the raw materials of the atomic putty in this technical solution include a photocuring resin and a photoinitiator. After scraping, it can be completely cured only by irradiating with light for two seconds, realizing the matte-curing flash-drying performance of the atomic putty; the main raw materials are photocuring resin, talcum powder, and barium sulfate, and the raw materials do not contain solvents, achieving zero VOC emissions; however, this technical solution does not disclose the specific composition and effect of the photocuring resin, resulting in limited application prospects.

[0004] Chinese Patent with publication number CN107858080A discloses a UV repair coating, which is prepared by mixing the following components in mass percentage: 10 - 99.1% of a compound containing an olefinic unsaturated double bond; 0.5 - 50% of a diluent; 0.01 - 10% of a free radical polymerization initiator; 0 - 80% of an auxiliary agent; wherein, the compound containing an olefinic unsaturated double bond is selected from one or more of unsaturated polyester, epoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyester acrylate resin and their modified products or derivatives. This coating is different from traditional UV coatings and can be used to repair damaged surfaces such as walls or floors. However, the filler content in this technical solution is relatively small, which may lead to poor repair effects. Summary of the Invention

[0005] In view of the above problems, the present invention provides an atomic putty based on ultraviolet curable resin, a preparation method thereof and an application thereof.

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

[0007] In the first aspect of the present invention, there is provided an atomic putty based on ultraviolet curable resin. By mass, the raw materials 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 ultraviolet curable resin includes a photocurable unsaturated polyester resin and a polyester acrylate; the mass ratio of the photocurable unsaturated polyester to the polyester acrylate is (6 - 10):(2 - 4), preferably 8:3;

[0009] The filler includes antioxidant / halloysite nanotubes / basalt fibers, nano calcium carbonate, and nano zirconia; the mass ratio of antioxidant / halloysite nanotubes / basalt fibers, 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, is purchased from Kunshan Kast Polymer Materials Co., Ltd., and the model is U - Cure 9215.

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

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

[0013] Preferably, the preparation method of the photocurable unsaturated polyester resin includes the following steps:

[0014] S1. Under nitrogen protection, a dibasic acid, phthalic anhydride, and a diol are subjected to a polycondensation reaction under the action 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 to obtain a saturated polyester resin;

[0016] S3. The saturated polyester resin and butyl acetate are mixed evenly, and isocyanate ethyl acrylate is added for reaction to obtain a photocurable unsaturated polyester resin.

[0017] In order to solve the problems that traditional two-component putties need to be prepared immediately before use and have a long curing time, in the present invention, the isocyanate group in ethyl isocyanate acrylate reacts with the saturated polyester resin to introduce unsaturated double bonds into the polyester resin, thereby enabling the unsaturated polyester resin to be cured by ultraviolet light. At the same time, the inventor of the present invention found that the obtained putty has good adhesion and flexibility, and it is speculated that this is because the formation of urethane bonds can form stronger chemical bonds with the substrate, and at the same time, flexible segments are introduced to increase the free volume between molecules.

[0018] However, the inventor of the present invention found that the putty has poor heat resistance, and it is speculated that this is due to the presence of thermally weak urethane bonds and unsaturated bonds. To solve this technical problem, the inventor of the present invention unexpectedly found that when a photocurable unsaturated polyester resin and a polyester acrylate are compounded, and poly(methyl methacrylate-co-methacrylic acid) is added at the same time, the obtained putty not only has excellent heat resistance, but also greatly improves the adhesion, flexibility and impact resistance of the putty. However, the inventor of the present invention also found that it is necessary to control the mass ratio of the ultraviolet-curable resin, the filler and poly(methyl methacrylate-co-methacrylic acid) to be (8-10):(7-10):1, otherwise it will lead to a decrease in the performance of the putty.

[0019] Preferably, in step S1, the dibasic acid 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.

[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 4:3:1.8:6:2.5:0.6.

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

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

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

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

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

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

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

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

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

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

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

[0034] Step 1: Immerse the basalt fiber completely 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, an alcohol solution of γ-methacryloxypropyltrimethoxysilane and an alkali solution solvent 1 evenly, stir and react, wash and dry after the reaction to obtain modified basalt fiber;

[0036] Step 3: Mix the halloysite nanotube and a γ-mercaptopropyltrimethoxysilane solution evenly, stir and react, wash and dry after the reaction to obtain modified halloysite nanotube;

[0037] Step 4: Disperse the antioxidant in ethanol, add the modified halloysite nanotube, ultrasonicate, and apply negative pressure by vacuum to obtain halloysite nanotube loaded with antioxidant;

[0038] Step 5: Mix the modified basalt fiber, halloysite carbon nanotube loaded with antioxidant and an alkaline solvent 2, stir and react, wash and dry after the reaction to obtain antioxidant / halloysite nanotube / basalt fiber.

[0039] In cold regions, due to the large temperature difference between day and night, when putty is subjected to sudden cold and heat changes, it is prone to cracking and peeling. To solve this technical problem, the inventor creatively prepared an antioxidant / halloysite nanotube / basalt fiber. Carbon-carbon double bonds were introduced onto the basalt fiber, and mercapto groups were introduced onto the halloysite nanotube. At the same time, the antioxidant was loaded in the halloysite nanotube. Through the reaction of carbon-carbon double bonds and mercapto groups, a composite of basalt fiber and halloysite nanotube was formed. Theoretically, during curing, the antioxidant / halloysite nanotube / basalt fiber can bend freely and show interweaving with each other to form a support structure, which can not only improve the flexibility of the putty, but also buffer temperature changes, reduce shrinkage, and reduce stress damage caused by thermal expansion and contraction. However, the inventor found that if only the antioxidant / halloysite nanotube / basalt fiber is used as a filler, 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 using the antioxidant / halloysite nanotube / basalt fiber cannot fully fill the micro-pores of the resin matrix. To solve this technical problem, the inventor unexpectedly found that when the filler includes antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate, and nano zirconia, the obtained putty has excellent adhesion, flexibility, impact resistance, and high and low temperature cycle resistance.

[0040] Preferably, the basalt fiber in step S1 is granular, and the average fiber length is 3-6 mm.

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

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

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

[0044] Preferably, the alcohol solution of γ-methacryloyloxypropyltrimethoxysilane in step 2 is composed of γ-methacryloyloxypropyltrimethoxysilane and ethanol with 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 °C, the rotation speed of the stirring reaction is 300-600 rpm, and the stirring reaction time is 8-12 h.

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

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

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

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

[0051] Preferably, in step 4, the antioxidant 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), preferably 1.5:1:100:3.

[0053] Preferably, in step 4, the time of ultrasonic treatment is 30 - 60 min, and the time of vacuum negative pressure is 30 - 60 min.

[0054] More preferably, in step 4, the time of ultrasonic treatment is 40 min, and the time of vacuum negative pressure is 40 min.

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

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

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

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

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

[0060] Preferably, the photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 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-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin diethyl ether; the mass ratio of 1-hydroxycyclohexyl phenyl ketone, 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-hydroxycyclohexyl phenyl ketone, 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 putty based on the ultraviolet-curable resin, comprising the following steps: uniformly mixing the ultraviolet-curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid), and photoinitiator.

[0064] The third aspect of the present invention provides the application of the putty based on the ultraviolet-curable resin in the fields of automobile repair, furniture manufacturing, and decoration.

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

[0066] 1. In the present invention, the isocyanate group in ethyl isocyanate acrylate reacts with the saturated polyester resin to introduce unsaturated double bonds into the polyester resin, thereby enabling the unsaturated polyester resin to be cured by ultraviolet light, and at the same time, the obtained putty has good adhesion and flexibility.

[0067] 2. The present invention uses a photocurable unsaturated polyester resin and a polyester acrylate for compounding, and at the same time adds poly(methyl methacrylate-co-methacrylic acid), and controls the mass ratio of the ultraviolet-curable resin, filler, and poly(methyl methacrylate-co-methacrylic acid) to be (8 - 10):(7 - 10):1. The obtained putty not only has excellent heat resistance, but also greatly improves the adhesion, flexibility, and impact resistance of the putty.

[0068] 3. When the filler in the present invention includes an antioxidant / halloysite nanotubes / basalt fibers, nano calcium carbonate, and nano zirconia, the obtained putty has excellent adhesion, flexibility, impact resistance, and high and low temperature cycle resistance. Specific embodiments

[0069] In order to have a clearer understanding of the technical features, objectives, and effects of the present invention, specific implementation embodiments will now be described in detail.

[0070] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to the following embodiments. The implementation conditions adopted 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 various implementation manners of the present invention can be combined with each other as long as they do not conflict with each other.

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

[0072] Example 1

[0073] An automotive putty based on ultraviolet (UV) curable resin, calculated by mass fraction, the raw materials consist of 30 parts of UV curable resin, 25 parts of filler, 3 parts of diluent, 3 parts of poly(methyl methacrylate - co - methacrylic acid), and 0.05 part of photoinitiator.

[0074] 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.

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

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

[0077] The preparation method of the photocurable unsaturated polyester resin is as follows:

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

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

[0080] S3. The saturated polyester resin and butyl acetate are mixed evenly, and isocyanate ethyl acrylate is added for reaction to obtain a photocurable unsaturated polyester resin.

[0081] The dibasic acid described 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 dibasic alcohol 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 the 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 temperature of the polycondensation reaction described in step S1 is 200 °C, and the time of the polycondensation reaction is 5 h.

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

[0085] The number-average molecular weight of the polycaprolactone diol is 2000, purchased from Xuzhou Yihuiyang New Materials Co., Ltd., model: PCL-2000.

[0086] The temperature of the polycondensation reaction described in step S2 is 260 °C, and the time of the polycondensation reaction is 3 h.

[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) described in step S3 is 1:1.2:0.03.

[0088] The temperature of the reaction substances described in step S3 is 60 °C, and the time of the reaction is 4 h.

[0089] The filler includes antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate, nano zirconia; the mass ratio of the antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate, nano zirconia is 18:4:1.

[0090] The particle size of the nano calcium carbonate is 20 nm, purchased from Ningbo Luofei Nano Technology Co., Ltd., product number: LF-CaCO3-N20.

[0091] The nano zirconia is purchased from Langfang Nako New Materials Technology Co., Ltd., model: ZO-P-3Y.

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

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

[0094] Step 2: Mix the acidified basalt fibers, dopamine hydrochloride, an alcohol solution of γ-methacryloxypropyltrimethoxysilane, and an alkaline solvent 1 evenly, stir and react. After the reaction, wash and dry to obtain modified basalt fibers;

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

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

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

[0098] The basalt fibers described in Step 1 are granular, with an average fiber length of 3 - 6 mm, purchased from Changsha North America Fuxin New Materials Technology Co., Ltd., model: 1000.

[0099] The acidification temperature described in Step 1 is 60 °C, and the acidification time is 3 h.

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

[0101] The alcohol solution of γ-methacryloxypropyltrimethoxysilane described in Step 2 is composed of γ-methacryloxypropyltrimethoxysilane and ethanol with a mass ratio of (2:100).

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

[0103] The temperature of the stirring reaction in Step 2 is 45 °C, the rotation speed of the stirring reaction is 500 rpm, and the stirring reaction time is 10 h.

[0104] The mass ratio of the halloysite nanotubes and the γ-mercaptopropyltrimethoxysilane solution in Step 3 is 1:40.

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

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

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

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

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

[0110] The time of ultrasonic treatment described in step 4 is 40 min, and the time of vacuum negative pressure is 40 min.

[0111] The mass ratio of the modified basalt fiber, halloysite carbon nanotubes loaded with antioxidant and basic solvent 2 described in step 5 is 1:3:100.

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

[0113] The temperature of the stirring reaction described in step 5 is 25 °C, the rotation speed of the stirring reaction is 80 rpm, and the time of the stirring reaction is 9 h.

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

[0115] The photoinitiator is a mixture of 1-hydroxycyclohexyl phenyl ketone (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 the 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzoin diethyl ether is 4:2:4.

[0116] The preparation method of the putty based on ultraviolet curable resin is as follows: mix the ultraviolet curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid) and photoinitiator evenly to obtain.

[0117] Example 2

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

[0119] The preparation method of the above-mentioned putty based on ultraviolet light curing resin is the same as that in Example 1.

[0120] Example 3

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

[0122] The preparation method of the above-mentioned putty based on ultraviolet light curing resin is the same as that in Example 1.

[0123] Comparative Example 1

[0124] The difference from Example 3 is that the polyester acrylate is replaced by a light-curable unsaturated polyester resin of equal mass; the rest are the same.

[0125] Comparative Example 2

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

[0127] Comparative Example 3

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

[0129] Comparative Example 4

[0130] The difference from Example 3 is that the filler is antioxidant / halloysite nanotube / basalt fiber; the rest are the same.

[0131] Comparative Example 5

[0132] The difference from Example 3 is that the nano zirconium oxide is replaced by nano calcium carbonate of the same mass; the rest are the same.

[0133] Comparative Example 6

[0134] The difference from Example 3 is that the antioxidant / halloysite nanotubes / basalt fibers are replaced with the same mass of halloysite nanotubes loaded with antioxidants; the rest are the same.

[0135] Comparative Example 7

[0136] The difference from Example 3 is that the preparation method of the antioxidant / halloysite nanotube / basalt fiber is as follows: Steps 1-4 are the same as those in Example 3; Step 5: Mix the modified basalt fiber and the halloysite carbon nanotube loaded with antioxidant to obtain; 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 ultraviolet curable resin, by mass, consists of 30 parts of ultraviolet curable resin, 41 parts of filler, 5.5 parts of diluent, 9 parts of poly(methyl methacrylate-co-methylacrylic acid), and 0.5 part of photoinitiator; the rest are the same.

[0139] Performance Test:

[0140] The putties of Examples 1-3 and Comparative Examples 1-8 based on ultraviolet curable resin were respectively applied to galvanized sheets with a thickness of 0.5 mm, and UV cured for 3 s at a curing energy of 1500 mJ / cm 2 to carry out crosslinking curing. After curing, the galvanized sheets were placed in a dry and ventilated place and dried for 24 hours, and then the following tests were carried out:

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

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

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

[0144] 4. Heat resistance: Place it at 160 °C for 10 h, cool it to room temperature, observe the coating film, if the coating film is not damaged, it is recorded as qualified, otherwise it is unqualified;

[0145] 5. Resistance to high and low temperatures: Place it at 60 °C for 8 h, take it out and place it at room temperature for 2 h, then place it at -60 °C for 8 h, take it out and place it at room temperature for 2 h, which is recorded as 1 cycle. After 30 cycles, no cracking or peeling occurs, it is recorded as qualified, otherwise it is unqualified.

[0146] The results are shown in Table 1:

[0147] Table 1 Performance test results of putties based on ultraviolet curable resins in Examples 1-3 and Comparative Examples 1-8

[0148]

[0149] As can be seen from Table 1, the putties based on ultraviolet curable resins in Examples 1-3 have good adhesion, flexibility, impact resistance, heat resistance and high and low temperature resistance;

[0150] In Comparative Example 1, the polyester acrylate was replaced with an equal mass of a photocurable unsaturated resin, and the obtained putty had decreased adhesion and flexibility, decreased impact resistance, and unqualified heat resistance;

[0151] In Comparative Example 2, the poly(methyl methacrylate-co-methacrylic acid) was replaced with an equal mass of polyester acrylate, and the obtained putty had decreased flexibility and impact resistance, and unqualified heat resistance;

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

[0153] In Comparative Example 4, the filler only contained antioxidant / halloysite nanotubes / basalt fibers, and the obtained putty had low adhesion, and also decreased flexibility and impact resistance, and unqualified high and low temperature resistance;

[0154] In Comparative Example 5, the nano-zirconia was replaced with an equal mass of nano-calcium carbonate, and the obtained putty had decreased adhesion, flexibility and impact resistance, and unqualified high and low temperature resistance;

[0155] In Comparative Example 6, the antioxidant / halloysite nanotubes / basalt fibers were replaced with an equal mass of halloysite nanotubes loaded with antioxidants, and the obtained putty had decreased adhesion and impact resistance, severely decreased flexibility, and unqualified heat resistance and high and low temperature resistance;

[0156] In Comparative Example 7, the modified basalt fibers and halloysite carbon nanotubes loaded with antioxidants were directly mixed, and the obtained putty had decreased adhesion, and severely decreased flexibility and impact resistance, and unqualified high and low temperature resistance;

[0157] In Comparative Example 8, the mass ratio of the ultraviolet curable resin, the filler and the poly(methyl methacrylate-co-methacrylic acid) was not within the range of (8-10):(7-10):1, and the obtained putty had severely decreased adhesion, flexibility and impact resistance, and unqualified high and low temperature resistance.

[0158] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than a limitation on the protection scope of the present invention. Any simple modification or equivalent replacement made by those of ordinary skill in the art to the technical solution of the present invention shall not depart from the essence and scope of the technical solution of the present invention.

Claims

1. An atomic putty based on ultraviolet curable resin, characterized in that, By mass parts, the raw materials 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; The ultraviolet curable resin includes a photocurable unsaturated polyester resin and a polyester acrylate; the mass ratio of the photocurable unsaturated polyester and the polyester acrylate is (6-10):(2-4); The filler includes antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate, and nano zirconia; the mass ratio of the antioxidant / halloysite nanotube / basalt fiber, nano calcium carbonate, and nano zirconia is (15-20):(2-6):

1.

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

1.

3. The putty based on ultraviolet curable resin according to claim 2, wherein, The preparation method of the photocurable unsaturated polyester resin includes the following steps: S1. Under nitrogen protection, a dibasic acid, phthalic anhydride, and a diol are subjected to a polycondensation reaction under the action 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 to obtain a saturated polyester resin; S3. The saturated polyester resin and butyl acetate are mixed evenly, and isocyanate acrylate ethyl is added for reaction to obtain a photocurable unsaturated polyester resin.

4. The putty based on ultraviolet curable resin according to claim 3, wherein In step S1, the dibasic acid 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 ultraviolet curable resin according to claim 1, characterized in that, The preparation method of the antioxidant / halloysite nanotube / basalt fiber includes the following steps: Step 1. The basalt fiber is completely impregnated in concentrated nitric acid for acidification, washed to neutrality, and dried to obtain acidified basalt fiber; Step 2. The acidified basalt fiber, dopamine hydrochloride, an alcohol solution of γ-methacryloxypropyltrimethoxysilane, and an alkali solution solvent 1 are mixed evenly, stirred and reacted, and after the reaction is completed, washed and dried to obtain modified basalt fiber; Step 3. The halloysite nanotube and a γ-mercaptopropyltrimethoxysilane solution are mixed evenly, stirred and reacted, and after the reaction is completed, washed and dried to obtain modified halloysite nanotube; Step 4. The antioxidant is dispersed in ethanol, the modified halloysite nanotube is added, ultrasonicated, and vacuum negative pressure is applied to obtain halloysite nanotube loaded with antioxidant; Step 5. The modified basalt fiber, halloysite carbon nanotube loaded with antioxidant, and an alkaline solvent 2 are mixed, stirred and reacted, and after the reaction is completed, washed and dried to obtain antioxidant / halloysite nanotube / basalt fiber.

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

100.

7. The putty based on ultraviolet curable resin according to any one of claims 1-6, characterized in that, The photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 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 ultraviolet curable resin according to claim 7, characterized in that, The photoinitiator is a mixture of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin diethyl ether; the mass ratio of 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin diethyl ether is (3-5):(1-3):(2-6).

9. The preparation method of the putty based on ultraviolet curable resin according to any one of claims 1-8, characterized in that It includes the following steps: Mix the ultraviolet curable resin, filler, diluent, poly(methyl methacrylate-co-methacrylic acid), and photoinitiator evenly to obtain the product.

10. Application of the putty based on ultraviolet curable resin according to any one of claims 1-8 in the fields of automobile repair and furniture manufacturing.

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