A light-cured quick repair putty and a preparation method thereof

Abstract

This application provides a photocurable quick-fix putty and its preparation method. The putty uses a functionalized modified resin as its core, combined with a MAP-POSS grafted modified photosensitive resin system and La... 3+ A three-dimensional hybrid nano-reinforcing phase, consisting of coordination-bridged one-dimensional activated BNNTs and two-dimensional ZrP nanosheets, is prepared by dispersion, degassing, and ball milling, in combination with a photoinitiator, additives, and fillers. This application effectively enhances the photocuring activity and substrate adhesion of the resin system through resin molecular structure design; improves the curing degree of thick coatings through MAP-POSS organic-inorganic hybrid modification; and significantly improves the mechanical properties and long-term protective performance of the system through rare-earth coordination-bridged three-dimensional hybrid nano-reinforcing phase. The photocurable quick-repair putty of this application achieves surface drying in 25 seconds and complete curing in 40 seconds, with a 98.2% curing degree for a 5mm thick base coat. It also possesses excellent mechanical properties and anti-aging properties, and the preparation process is simple and easy to promote and implement.

Description

Technical Field

[0001] This application belongs to the field of polymer materials technology, specifically relating to a light-curing quick-fix putty and its preparation method. Background Technology

[0002] In existing technologies, automotive sheet metal repair putty (also known as body filler or sheet metal putty) is the core filling and leveling material for repairing automotive body damage. It can accurately fill sheet metal dents, scratches, and rust defects, restore the flatness of the body, and provide a stable adhesion base for subsequent painting. It directly determines the construction efficiency, repair accuracy, and long service life of sheet metal repair, and is an indispensable key material for sheet metal repair processes in the automotive aftermarket.

[0003] While existing mainstream two-component unsaturated polyester sheet metal putty offers improvements in hardness and thickness compared to ordinary putty, it suffers from inherent defects: First, curing depends on the precise ratio of hardener to base agent, which is difficult to control in actual construction, easily leading to irreversible quality problems such as incomplete curing and brittleness; second, curing efficiency is low, requiring 20-30 minutes for complete curing at room temperature (20℃), with further extended curing time at low temperatures, severely restricting the efficiency of quick automotive repairs; third, overall stability is insufficient, and long-term exposure to vibration, thermal cycling, and humid aging can easily cause cracking and peeling off from the substrate, making it difficult to guarantee service life.

[0004] Therefore, in order to comprehensively solve the many technical pain points of existing putties, it is urgent to develop a light-curing quick-repair putty that is single-component and requires no mixing, can be fully cured in a single 5mm thick coat, dries quickly in tens of seconds, and combines high hardness and flexibility, strong adhesion, weather resistance and crack resistance, so as to comprehensively improve the construction efficiency and long-term stability of automotive sheet metal repair. Summary of the Invention

[0005] This application aims to address the technical problems of existing two-component putty for automotive sheet metal repair, such as difficulty in controlling the mixing ratio, low curing efficiency, easy incomplete curing, irreversible quality defects such as brittleness and cracking, and easy cracking and peeling after long-term use. It also addresses the poor deep curing performance of existing UV-cured putty, the tendency for single coating thicknesses exceeding 1mm to be surface dry but not dry inside, the inability to meet the repair needs of 5mm thick coatings, and the existence of imbalance between hardness and flexibility, insufficient adhesion to metal substrates, and poor weather resistance and crack resistance. Therefore, this application proposes a UV-cured quick repair putty and its preparation method.

[0006] To address the technical problems raised in this application, this application also proposes a method for preparing a light-curing quick-repair putty.

[0007] In order to solve the technical problems raised in this application, this application also proposes a construction method for light-curing quick-repair putty.

[0008] This application adopts the following solution: a light-curing quick-repair putty, which, by weight, is composed of the following components:

[0009] Photosensitive resin A 320-400 parts, photoinitiator 6-9 parts, dispersant 5-7 parts, defoamer 1-2 parts, leveling agent 0.5-1.5 parts, filler 330-397 parts, accelerator 2-4 parts, and ultraviolet absorber 0.5-1 part;

[0010] The filler, by weight, comprises the following components:

[0011] Titanium dioxide 2.2-2.5 parts, fumed silica 5-9 parts, talc 310-365 parts, nano-reinforcing phase 14-19 parts, lanthanum chloride 1-1.5 parts;

[0012] The photosensitive resin A is obtained by grafting a functionalized modified resin matrix with methacryloxypropyl cage-type silsesquioxane. The functionalized modified resin matrix is ​​obtained by polymerizing allyl ether, phosphate ester, polyol, and polyacid.

[0013] The nano-reinforcing phase is a lanthanum-coordinated bridging multidimensional modified nanocomposite.

[0014] In actual implementation, the nano-reinforcing phase is La. 3+ Coordination-bridged one-dimensional activated BNNTs-two-dimensional ZrP nanosheets three-dimensional hybrid nanocomposite.

[0015] In actual implementation, the talc powder is obtained by compounding 3000-mesh talc powder and 1250-mesh talc powder at a mass ratio of 1:3.4. The talc powder undergoes surface modification treatment, which includes the following steps: talc powder of a preset ratio and specification, silane coupling agent KH-570, and anhydrous ethanol are sequentially added to a high-speed mixer at a mass ratio of 100:1:2. After dispersion at 110℃ and 1200rpm for 45 minutes, modified crude talc powder is obtained. The modified crude talc powder is then transferred to a vacuum drying oven for vacuum drying and sieved to a preset mesh size, thus completing the modification treatment of the talc powder.

[0016] In actual implementation, the photoinitiator is obtained by compounding photoinitiator 1173, photoinitiator TPO, and photoinitiator 819 in a mass ratio of 1:1:1.

[0017] In some feasible embodiments, the preparation method of the photosensitive resin A includes the following steps:

[0018] Step 101. The functionalized modified resin matrix, styrene, TBHQ, MAP-POSS and free radical initiator azobisisobutyronitrile (AIBN) are added to the dilution vessel in a predetermined ratio. The reaction is carried out at 80°C, nitrogen flow rate of 50 mL / min and 100 rpm-150 rpm for 2 hours. The reaction system is then cooled to 50°C and kept at that temperature to obtain the crude grafted modified resin.

[0019] The addition amount of azobisisobutyronitrile (AIBN) is 0.8%-1.2% of the total mass of the system.

[0020] Azobisisobutyronitrile (AIBN) is added when the reaction system is heated to 60°C, and after stirring evenly, the temperature is further increased to 80°C.

[0021] Step 102. Add 1,4-naphthoquinone, antioxidant 1010, antioxidant 168 and TBHQ into a dilution vessel in a predetermined ratio. Stir for 40 minutes at 45°C, nitrogen flow rate of 15 mL / min and 100-150 rpm to obtain photosensitive resin A.

[0022] In some feasible embodiments, the method for preparing the functionalized modified resin matrix includes the following steps:

[0023] Step 201. Ethylene glycol, neopentyl glycol, tetrahydrophthalic anhydride, and TBHQ are added to a reaction vessel in a predetermined ratio. The mixture is reacted at 0.02 MPa, nitrogen flow rate of 50 mL / min, 200 rpm-300 rpm, and 160 °C for 1 hour to obtain a molten material. The molten material is then reacted at 210 °C, -0.095 MPa, and under oil-water separation conditions for 3 hours to obtain a primary esterified polycondensate.

[0024] Step 202. Cool the primary esterified condensate obtained in step 201 to 90°C, and add maleic anhydride in a predetermined ratio to the primary esterified condensate. React for 4 hours under the conditions of 0.02 MPa, 210°C, and 200 rpm-300 rpm to obtain the secondary esterified condensate.

[0025] Step 203. Cool the secondary esterified condensate obtained in step 202 to 165°C, and add the pre-prepared ratio of trimethylolpropane diallyl ether and hydroxyethyl methacrylate phosphate to the reaction system. After reacting for 3 hours at 140°C and 150-250 rpm, the functionalized modified resin matrix is ​​obtained.

[0026] In some feasible embodiments, in step 201, the top temperature of the distillation column is ≤102℃, and the acid value is sampled and tested every 1 hour until the acid value is 25mgKOH / g-28mgKOH / g;

[0027] In step 202, the acid value is sampled and tested every 1 hour until the acid value stabilizes at 40mgKOH / g-50mgKOH / g;

[0028] In step 203, samples are taken every 1 hour to test the acid value and viscosity. When the acid value stabilizes at 20mgKOH / g-25mgKOH / g and is diluted with solvent to a solid content of 50%, the viscosity is measured at 25°C using a cone-plate viscometer at a value of 620mPa・s-680mPa・s. At this point, heating is stopped and rapid cooling is initiated.

[0029] In some feasible embodiments, the preparation method of the nano-reinforced phase includes the following steps:

[0030] Step 301. Add ZrP nanosheets and deionized water into an ultrasonic reactor at a mass ratio of 1:999. After ultrasonication for 30 minutes at an ultrasonic power of 300W and an ice bath temperature of 5℃, ZrP colloid is obtained.

[0031] Step 302. Activated BNNTs and deionized water are added to an ultrasonic reactor at a mass ratio of 1:499. After ultrasonication for 30 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, activated BNNTs colloid is obtained. Then, the ZrP colloid prepared in step 301 is added to the activated BNNTs colloid. After ultrasonication for 10 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, a composite colloid is obtained.

[0032] Step 303. The composite colloid prepared in step 302 and the 1.25wt% lanthanum chloride solution are added to a stirred tank in a mass ratio of 400:1. The mixture is stirred at room temperature and 500 rpm for 30 min to obtain the composite reaction solution.

[0033] Step 304. After centrifuging the composite reaction solution obtained in step 303, collect the precipitate and wash it three times alternately with deionized water and anhydrous ethanol. After washing, the precipitate is vacuum dried at 60℃ and gauge pressure -0.095MPa for 12 hours, ground in an agate mortar and passed through an 800-mesh standard sieve to obtain the nano-reinforced phase.

[0034] In some feasible embodiments, the preparation method of activated BNNTs includes the following steps:

[0035] Boron nitride nanotube powder with a pre-prepared ratio was spread evenly on a quartz sample stage. After controlling the layer thickness to ≤1mm, the sample was placed in the discharge chamber of a cold plasma treatment instrument. The chamber was closed and evacuated to an absolute pressure ≤10Pa and held for 10min. Pure oxygen was introduced until the chamber pressure stabilized at 30Pa and the oxygen flow rate was 10mL / min. The discharge power was set to 100W, and each treatment lasted 2min. The treatment was repeated 3 times. After each treatment, the vacuum was broken and the powder was taken out. The powder was turned over with a glass rod moistened with anhydrous ethanol until there was no powder accumulation before the next treatment. After all treatments were completed, the powder was vacuum dried at 60℃ and a gauge pressure of -0.095MPa for 12h to obtain activated BNNTs.

[0036] In some feasible embodiments, the preparation method of ZrP nanosheets includes the following steps:

[0037] Step 401. Add α-zirconium phosphate powder and deionized water into the reaction vessel at a mass ratio of 1:200, and stir for 40 minutes at room temperature and 500 rpm to obtain the emulsion system.

[0038] Step 402. Add 0.1 mol / L tetrabutylammonium hydroxide solution dropwise to the emulsion system, control the molar ratio of α-zirconium phosphate and tetrabutylammonium hydroxide to be 2:1, stir for 12 h in an ice bath at 0℃ and 400 rpm, and then sonicate for 1 h in an ice bath at 300 W and 10℃ to obtain a transparent system.

[0039] Step 403. After centrifuging the transparent system prepared in step 402 at 5000 rpm for 20 min, take the supernatant and add 0.1 mol / L dilute hydrochloric acid dropwise until the pH of the system stabilizes at 5.5, resulting in a white flocculent precipitate; after centrifuging the precipitate at 6000 rpm for 15 min, remove the supernatant, and then wash and vacuum dry to obtain ZrP nanosheets.

[0040] To address the technical problems raised in this application, this application also provides a method for preparing a light-curing quick-repair putty, comprising the following steps:

[0041] Step 501. Add the pre-mixed photosensitive resin A into a stirred tank and disperse it for 10 minutes at 25℃-30℃ and 1200rpm to obtain the liquid phase body. Then add the pre-mixed dispersant BYK-110, defoamer BYK-066N, leveling agent BYK-333, accelerator PM-2, ultraviolet absorber UV-327, photoinitiator, and nano-reinforcing phase into the liquid phase body in one go. Stir for 30 minutes at 15℃ in a water bath, in the dark, and at 1800rpm to obtain the premixed resin liquid.

[0042] Step 502. Add fumed silica HL-200, rutile titanium dioxide R-902, talc and lanthanum chloride to the premixed resin liquid prepared in step 501 in a preset ratio. After dispersing at room temperature and 2800rpm-3000rpm for 45min, a coarse dispersion slurry is obtained.

[0043] Step 503. Transfer the coarse dispersion slurry prepared in step 502 to a vacuum degassing machine, stir for 20 minutes under the conditions of constant temperature of 25℃, -0.09MPa, and 1200rpm in a water bath, and then break the vacuum to obtain a fine dispersion slurry; then transfer the fine dispersion slurry to a horizontal ball mill and ball mill until the slurry fineness is ≤20μm to obtain a light-curing quick-repair putty.

[0044] To address the technical problems raised in this application, this application also provides a method for applying a light-curing quick-repair putty, which includes the following steps:

[0045] Step 601. Assemble 80#-120# dry sandpaper onto a pneumatic eccentric grinder and grind away the old coating and rust layer of the repair area (automotive sheet metal) until a uniform metal substrate is exposed. Grind the intact coating around the repair area to create a feathered edge with a width ≥30mm and a slope ≤30°. Then, according to the weight ratio of clean non-woven cloth to automotive sheet metal degreasing agent 1:(2-3), perform two degreasing treatments on the repair area and the surrounding 50mm range. For the first time, wipe unidirectionally with a non-woven cloth soaked in degreasing agent. For the second time, immediately wipe dry with a clean dry non-woven cloth. Control the surface roughness of the substrate Ra to 25μm-50μm. The construction environment temperature should be 15℃-35℃, the relative humidity ≤75%, and the surface temperature of the substrate should be more than 3℃ higher than the ambient dew point.

[0046] Step 602. In a light-protected environment, take the light-curing quick-repair putty provided in this application and place it on a light-protected mixing board. The amount of material taken at one time should be ≤500g. Stir for 1min-2min at room temperature and 300rpm-500rpm until the system is uniform. No hardener or thinner needs to be added. First, apply the putty to the substrate surface with a thickness of 0.5mm-1mm under pressure to form a dense base coating. Then, complete the thick coating filling in 1-2 layers. The maximum thickness of a single coating should be ≤5mm, and the total coating time should be ≤10min. Ensure that the putty is fully filled and completely wetted with the substrate without air bubbles.

[0047] Step 603. Use a dominant wavelength of 395nm and an optical power density of 800mW / cm². 2 -1200mW / cm 2The UV-LED curing lamp is used, and the vertical distance between the curing lamp and the putty surface is controlled at 15cm-20cm. It is moved at a uniform speed of 1cm / s-3cm / s along the repair area. The irradiation time is matched according to the coating thickness: ≤1mm thickness, ≥25s irradiation time; 1mm-3mm thickness, ≥30s irradiation time; 3mm-5mm thickness, ≥40s irradiation time, until the putty is completely cured and the Shore hardness is ≥85HD.

[0048] Step 604. After curing, first use 80#-120# dry sandpaper with a pneumatic eccentric sander with a rated speed of 4000rpm-6000rpm for rough sanding and shaping, then use 180#-240# dry sandpaper for fine sanding and transition, and finally use 320# dry sandpaper for fine sanding until the surface is smooth and without joint steps; after sanding, use a dust gun to remove dust, and then clean and degrease again according to the weight ratio of clean non-woven cloth to automotive sheet metal degreasing agent 1: (2-3), and you can directly connect to the subsequent automotive painting process.

[0049] Compared with the prior art, this application has the following beneficial effects:

[0050] This application provides a photocurable quick-fix putty and its preparation method. The putty uses a functionalized modified resin as its core, combined with a MAP-POSS grafted modified photosensitive resin system and La... 3+ A three-dimensional hybrid nano-reinforcing phase, composed of coordination-bridged one-dimensional activated BNNTs and two-dimensional ZrP nanosheets, is prepared by dispersion, degassing, and ball milling processes, in conjunction with a photoinitiator, additives, and fillers. This application significantly improves the photocuring performance and substrate adhesion of the putty through resin molecular structure design, significantly increases the curing speed, and extends the service life of the putty. MAP-POSS organic-inorganic hybrid modification significantly improves the complete curing degree during thick-coat application of the putty. The rare-earth coordination-bridged three-dimensional hybrid nano-reinforcing phase achieves simultaneous improvement in both the material's mechanical properties and long-term protective performance. The light-curing quick-repair putty of this application can achieve surface drying in 25 seconds and complete curing in 40 seconds. The curing degree of a 5mm thick base coat reaches 98.2%. It also has a 3H pencil hardness, 0-level adhesion, 55cm impact strength and 1mm flexibility. It still maintains excellent performance after 1000h of damp heat aging, 1000h of neutral salt spray and 100 cycles of hot and cold. It is superior to mainstream products on the market and can be widely used in the rapid repair of automotive sheet metal. It has the advantages of controllable preparation process, high construction efficiency, excellent comprehensive performance and easy promotion and implementation. Attached Figure Description

[0052] Figure 1 This is a comparison chart of the curing times of the photocurable putty prepared in Examples 1-3 and Comparative Examples 1-8 of this application;

[0053] Figure 2 These are comparison images of the curing degree of 5mm thick coatings of the light-curing putty prepared in Examples 1-3 and Comparative Examples 1-8 of this application;

[0054] Figure 3 This is a comparison chart of the comprehensive mechanical properties of the light-cured putty prepared in Example 2, Comparative Example 1, Comparative Example 2, and Comparative Example 4 of this application after curing;

[0055] Figure 4 This is a product image of the light-cured putty prepared in Example 2 of this application;

[0056] Figure 5 This is a construction state diagram of the thick coating stage of the light-cured putty prepared in Example 2 of this application;

[0057] Figure 6 This is a construction state diagram of the curing stage of the light-curing putty prepared in Example 2 of this application. Detailed Implementation

[0058] Combined with Examples 1-3, Comparative Examples 1-8, Figures 1 to 6 The content shown further illustrates the technical solution proposed in this application. Example 1

[0059] [1] The preparation method of the functionalized modified resin matrix includes the following steps:

[0060] Step 201. According to the component table shown in Table 1, ethylene glycol, neopentyl glycol, tetrahydrophthalic anhydride, and TBHQ are added to the reactor in the preset ratio. After reacting for 1 hour at 0.02 MPa, nitrogen flow rate of 50 mL / min, 300 rpm, and 160 °C, the molten material is obtained. Then, the molten material is reacted for 3 hours at 210 °C, -0.095 MPa, and oil-water separation to obtain the primary esterified condensate.

[0061] In the oil-water separator, the top temperature of the distillation column is ≤102℃. The acid value is sampled and tested every 1 hour until the acid value reaches 25mgKOH / g-28mgKOH / g, at which point the reaction is terminated.

[0062] Step 202. Cool the primary esterified condensate obtained in step 201 to 90°C, and add maleic anhydride in a predetermined ratio to the primary esterified condensate. React for 4 hours under the conditions of 0.02 MPa, 210°C and 300 rpm to obtain the secondary esterified condensate.

[0063] The acid value was measured every 1 hour until the acid value stabilized at 40mgKOH / g-50mgKOH / g, at which point the reaction was terminated.

[0064] Step 203. Cool the secondary esterified condensate obtained in step 202 to 165°C, and add the pre-prepared ratio of trimethylolpropane diallyl ether and hydroxyethyl methacrylate phosphate to the reaction system. After reacting at 140°C and 250 rpm for 3 hours, the functionalized modified resin matrix is ​​obtained.

[0065] The acid value and viscosity were measured every 1 hour. When the acid value stabilized at 20mgKOH / g-25mgKOH / g and was diluted with solvent to a solid content of 50%, the viscosity was measured at 25℃ using a cone-plate viscometer at a value of 620mPa・s-680mPa・s, at which point the reaction was terminated.

[0066] [2] The preparation method of photosensitive resin A includes the following steps:

[0067] Step 101. According to the component table shown in Table 1, add the functionalized modified resin matrix, styrene, TBHQ, MAP-POSS and free radical initiator azobisisobutyronitrile (AIBN) into the dilution vessel in the preset ratio. After reacting for 2 hours at 80℃, nitrogen flow rate of 50mL / min and 150rpm, cool the reaction system to 50℃ and keep it at that temperature to obtain the crude grafted modified resin.

[0068] Step 102. Add 1,4-naphthoquinone, antioxidant 1010, antioxidant 168 and TBHQ into a dilution vessel in a predetermined ratio. Stir for 40 minutes at 45°C, nitrogen flow rate of 15 mL / min and 150 rpm to obtain photosensitive resin A.

[0069] [3] The preparation method of activated BNNTs includes the following steps:

[0070] Boron nitride nanotube powder of a pre-prepared ratio was spread evenly on a quartz sample stage. After controlling the layer thickness to 0.8 mm, it was placed in the discharge chamber of a cold plasma treatment instrument. The chamber was closed and evacuated to an absolute pressure of 9 Pa and held for 10 min. Pure oxygen was introduced until the chamber pressure stabilized at 30 Pa and the oxygen flow rate was 10 mL / min. The discharge power was set to 100 W, and each treatment lasted 2 min. The treatment was repeated 3 times. After each treatment, the vacuum was broken and the material was taken out. The material was turned over with a glass rod moistened with anhydrous ethanol until there was no powder accumulation before the next treatment. After all treatments were completed, the powder was vacuum dried at 60 °C and a gauge pressure of -0.095 MPa for 12 h to obtain activated BNNTs.

[0071] [4] The preparation method of ZrP nanosheets includes the following steps:

[0072] Step 401. Add α-zirconium phosphate powder and deionized water into the reaction vessel at a mass ratio of 1:200, and stir for 40 minutes at room temperature and 500 rpm to obtain the emulsion system.

[0073] Step 402. Add 0.1 mol / L tetrabutylammonium hydroxide solution dropwise to the emulsion system, control the molar ratio of α-zirconium phosphate and tetrabutylammonium hydroxide to be 2:1, stir for 12 h in an ice bath at 0℃ and 400 rpm, and then sonicate for 1 h in an ice bath at 300 W and 10℃ to obtain a transparent system.

[0074] Step 403. After centrifuging the transparent system prepared in step 402 at 5000 rpm for 20 min, take the supernatant and add 0.1 mol / L dilute hydrochloric acid dropwise until the pH of the system stabilizes at 5.5, resulting in a white flocculent precipitate; after centrifuging the precipitate at 6000 rpm for 15 min, remove the supernatant, and then wash and vacuum dry to obtain ZrP nanosheets.

[0075] [5] The preparation method of the nano-reinforced phase includes the following steps:

[0076] Step 301. Add ZrP nanosheets and deionized water into an ultrasonic reactor at a mass ratio of 1:999. After ultrasonication for 30 minutes at an ultrasonic power of 300W and an ice bath temperature of 5℃, ZrP colloid is obtained.

[0077] Step 302. Activated BNNTs and deionized water are added to an ultrasonic reactor at a mass ratio of 1:499. After ultrasonication for 30 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, activated BNNTs colloid is obtained. Then, the ZrP colloid prepared in step 301 is added to the activated BNNTs colloid. After ultrasonication for 10 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, a composite colloid is obtained.

[0078] Step 303. The composite colloid prepared in step 302 and the 1.25wt% lanthanum chloride solution are added to a stirred tank in a mass ratio of 400:1. The mixture is stirred at room temperature and 500 rpm for 30 min to obtain the composite reaction solution.

[0079] Step 304. After centrifuging the composite reaction solution obtained in step 303, collect the precipitate and wash it three times alternately with deionized water and anhydrous ethanol. After washing, the precipitate is vacuum dried at 60℃ and gauge pressure -0.095MPa for 12 hours, ground in an agate mortar and passed through an 800-mesh standard sieve to obtain the nano-reinforced phase.

[0080] [6] The preparation method of light-cured quick-repair putty includes the following steps:

[0081] Step 501. According to the component table shown in Table 2, add photosensitive resin A into a stirred tank and disperse it for 10 minutes at 28°C and 1200 rpm to obtain the liquid phase body; then add the pre-proportioned dispersant, defoamer, leveling agent, accelerator, ultraviolet absorber, photoinitiator, and nano-reinforcing phase to the liquid phase body in one go, and stir for 30 minutes at 15°C in a water bath, in the dark, and at 1800 rpm to obtain the premixed resin liquid;

[0082] Step 502. According to the component table shown in Table 1, add fumed silica, rutile titanium dioxide, talc and lanthanum chloride to the premixed resin liquid prepared in step 501 in a preset ratio. After dispersing at room temperature and 3000 rpm for 45 min, a coarse dispersion slurry is obtained.

[0083] Step 503. Transfer the coarse dispersion slurry prepared in step 502 to a vacuum degassing machine, stir for 20 minutes under the conditions of constant temperature of 25℃, -0.09MPa, and 1200rpm in a water bath, and then break the vacuum to obtain a fine dispersion slurry; then transfer the fine dispersion slurry to a horizontal ball mill and ball mill until the slurry fineness is ≤20μm to obtain a light-curing quick-repair putty. Example 2

[0084] The difference between Example 2 and Example 1 is that the components of the light-curing quick-repair putty are modified according to the component tables shown in Tables 1 and 2, while the rest of the process formula remains unchanged. Example 3

[0085] The difference between Example 3 and Example 1 is that the components of the light-curing quick-repair putty are modified according to the component tables shown in Tables 1 and 2, while the rest of the process formula remains unchanged.

[0086] Comparative Example 1

[0087] The difference between Comparative Example 1 and Example 2 is that: a commercially available two-component automotive body filler (DuPont Automotive Paint - Paimi 2K Body Filler - Two-component P5100 Atomic Putty) was used, and the photosensitive resin A system and nano-reinforcing phase system in Example 2 were not used. Instead, a commercially available two-component body filler was used for the ordinary unsaturated polyester system cured by traditional cyclohexanone peroxide.

[0088] Comparative Example 2

[0089] The difference between Comparative Example 2 and Example 2 is as follows: As shown in the component table in Table 2, in the preparation of photosensitive resin A, MAP-POSS in step 101 is removed and supplemented with styrene; in the preparation of photocurable quick-fix putty, the nano-reinforcing phase in step 501 is replaced with an equal mass of fumed silica, and the amount of talc powder is adjusted to supplement the system, while the rest of the process formulation remains unchanged.

[0090] Comparative Example 3

[0091] The difference between Comparative Example 3 and Example 2 is that, as shown in the component table in Table 2, in the preparation of photosensitive resin A, MAP-POSS in step 101 is removed and made up with styrene, while the rest of the process formulation remains unchanged.

[0092] Comparative Example 4

[0093] The difference between Comparative Example 4 and Example 2 is that, as shown in the component table in Table 2, the nano-reinforcing phase in step 501 is replaced with an equal amount of nano-mixture, which is obtained by compounding activated BNNTs and ZrP nanosheets in a mass ratio of 1:1, while the rest of the process formulation remains unchanged.

[0094] Comparative Example 5

[0095] The difference between Comparative Example 5 and Example 2 is that, as shown in the component table in Table 2, the nano-reinforcing phase in step 501 is replaced with an equal amount of talc powder, while the rest of the process formulation remains unchanged.

[0096] Comparative Example 6

[0097] The difference between Comparative Example 6 and Example 2 is that, as shown in the component table in Table 2, step 303 (without La) was omitted during the preparation of the nano-reinforced phase. 3+ (Coordination bridging), the rest of the process formulation remains unchanged.

[0098] Comparative Example 7

[0099] The difference between Comparative Example 7 and Example 2 is that, as shown in the component table in Table 2, step 301 (without ZrP nanosheets) was omitted in the preparation of the nano-reinforced phase, while the rest of the process formulation remained unchanged.

[0100] Comparative Example 8

[0101] The difference between Comparative Example 8 and Example 2 is that, as shown in the component table in Table 2, step 302 (without activated BNNTs) was removed during the preparation of the nano-reinforced phase, while the rest of the process formulation remained unchanged.

[0102] Table 1. Component A of the photosensitive resin in Examples 1-3

[0103]

[0104] Table 2. Components of UV-cured quick-repair putty

[0105]

[0106] Continued from Table 2

[0107]

[0108] The photocurable materials prepared in Examples 1-3 and Comparative Examples 1-8 were tested according to the contents shown in Table 3 below, and the corresponding test results are shown in Table 4 below.

[0109] Table 3 Test Items

[0110]

[0111] Table 4 Test Results

[0112]

[0113] Continued from Table 4

[0114]

[0115] Table 5. Material Source Details for Examples 1-3 and Comparative Examples 1-8

[0116]

[0117]

[0118] From Table 4, Figures 1-3 The test results show that, in Examples 1-3, the photosensitive resins A and La obtained by functionalizing the resin matrix and grafting with MAP-POSS are effective. 3+ The coordination-bridged one-dimensional-two-dimensional hybrid nano-reinforcing phase, along with the matching photocurable quick-repair putty preparation process, constructs a synergistic system of highly active photosensitive crosslinked resin matrix and nano-reinforcing phase, effectively solving the technical problems of slow curing speed, poor deep curing of thick coatings, and difficulty in simultaneously achieving mechanical properties and weather resistance and corrosion resistance in traditional automotive sheet metal putty.

[0119] Specifically, in the preparation of the functionalized modified resin matrix, a three-step esterification polycondensation process was used to achieve precise control of the resin molecular structure: First, through the esterification polycondensation of ethylene glycol, neopentyl glycol, and tetrahydrophthalic anhydride, a basic linear molecular chain with an alicyclic structure was constructed, providing basic rigidity and weather resistance for the resin matrix; Second, through the grafting reaction of maleic anhydride, highly active unsaturated double bonds were precisely introduced into the molecular chain, providing sufficient reaction sites for subsequent photocuring and crosslinking, while acid value monitoring ensured the stability and controllability of the reaction; Third, through the grafting modification of trimethylolpropane diallyl ether and hydroxyethyl methacrylate phosphate, on the one hand, the allyl ether structure was introduced to improve the air-drying properties and crosslinking activity of the resin, and on the other hand, the polar groups of phosphate ester were introduced, which can form strong chemical bonds with the oxide layer on the surface of the metal substrate, improving the interfacial adhesion between the putty and the substrate from the molecular level. The cross-cut adhesion of Examples 1-3 all reached the optimal level 0, which is far superior to the comparative examples.

[0120] Furthermore, during the preparation of photosensitive resin A, the performance of the resin crosslinking network was significantly improved by graft copolymerization of MAP-POSS with the functionalized modified resin matrix. MAP-POSS molecules possess photopolymerizable methacryloyloxy groups, which, under the action of a photoinitiating system, can simultaneously undergo free radical copolymerization with the unsaturated double bonds of the resin matrix and the styrene reactive diluent, chemically bonding the inorganic Si-O-Si cage structure into the three-dimensional crosslinking network of the resin. On one hand, the cage-like POSS structure can significantly improve the free radical utilization efficiency and crosslinking network density of the resin system, increasing the curing depth of the putty during thick coating. In Example 2, the curing degree of the 5mm thick undercoat reached 98.2%, far exceeding the 62.3% of Comparative Example 2. On the other hand, the inorganic cage structure can endow the resin matrix with excellent rigidity, heat resistance, and weather resistance, while reducing curing shrinkage and preventing cracking and peeling of the putty after curing, forming a synergistic reinforcing effect with the nano-reinforcing phase.

[0121] Furthermore, in the preparation of the nano-reinforcing phase, a hybrid nanostructure of one-dimensional tubular-two-dimensional sheet synergy was constructed through a process of cold plasma activation-intercalation exfoliation-rare earth ion coordination bridging. First, boron nitride nanotubes were surface-activated using cold plasma (oxygen plasma) to introduce a large number of active hydroxyl groups onto their surface without damaging the nanotube bulk structure, thereby improving the nanotubes' reactivity and dispersibility. Second, α-zirconium phosphate was intercalated and exfoliated using tetrabutylammonium hydroxide to prepare single-layer or few-layer ZrP nanosheets, retaining their ultra-high aspect ratio and surface active hydroxyl groups. Finally, La... 3+ The coordination bridging effect of La allows for the hybridization of activated BNNTs with ZrP nanosheets, utilizing La 3+ The empty f orbitals form stable coordination bonds with the hydroxyl groups on the surfaces of the two nanomaterials, which not only avoids the entanglement and aggregation of one-dimensional nanotubes and the stacking and aggregation of two-dimensional nanosheets, but also greatly improves the dispersion uniformity of nanofillers in the resin matrix, and constructs a continuous mechanical reinforcement network and a disordered network structure that blocks corrosion.

[0122] Furthermore, this hybrid nano-reinforcing phase and the photosensitive resin A matrix exhibit excellent synergistic effects: on the one hand, the one-dimensional-two-dimensional hybrid nanostructure can form an efficient stress transfer network in the resin matrix. Under stress, a large amount of impact energy is dissipated through crack bridging of activated BNNTs and crack deflection effect of ZrP nanosheets, achieving a simultaneous improvement in putty hardness, impact strength, and flexibility. In Example 2, the pencil hardness can reach 3H, the impact strength against a 1kg hammer is 55cm, and the flexibility is 1mm, which is far superior to the commercially available Comparative Example 1 and other comparative examples; on the other hand... On the other hand, the layer barrier effect of ZrP nanosheets and the overlapping effect of activated BNNTs can form a dense labyrinth barrier in the resin matrix, which greatly prolongs the penetration path of corrosive media. At the same time, the phosphate ester groups of the resin matrix and the polar groups of the nanofiller can form strong hydrogen bond anchoring with the surface of the metal substrate, which significantly improves the long-term service stability of the putty. After 1000h of damp heat aging, 1000h of neutral salt spray, and 100 cycles of hot and cold, there were no failure phenomena such as blistering, corrosion, cracking, or peeling, and the performance far exceeds that of traditional commercially available products.

[0123] Meanwhile, through the synergistic optimization of formulation and process, Examples 1-3 achieved a perfect balance between ultra-fast curing and high performance. The surface drying time of Example 2 is only 25s and the complete curing time is only 40s. Compared with commercially available two-component putty (900s for surface drying and 1500s for complete curing), the curing efficiency is improved by more than 30 times, which greatly shortens the construction cycle of automotive sheet metal repair and effectively solves the technical problems of slow curing and low construction efficiency of traditional sheet metal putty.

[0124] In Comparative Example 1, a commercially available two-component sheet metal putty was used, eliminating the photosensitive resin A system and nano-reinforced phase system from Example 2, and using a conventional unsaturated polyester system cured with cyclohexanone peroxide. First, traditional unsaturated polyester resins rely on redox systems to initiate free radical polymerization, resulting in low initiation efficiency and weak double bond crosslinking activity. This leads to extremely slow putty crosslinking and curing speeds, with surface drying time reaching 900s and complete curing time reaching 1500s, far exceeding the 25s and 40s of Example 2, respectively, making rapid repair of automotive sheet metal impossible. Second, ordinary unsaturated polyester resins have not undergone functional modification, failing to introduce phosphate ester polar groups, allyl ether air-drying structures, and rigid-flexible synergistic molecular chain segments. Consequently, they cannot form strong chemical bonds and hydrogen bond anchoring with the metal substrate, resulting in weak interfacial adhesion. Cross-cut adhesion is only grade 1, and after 1000 hours of damp heat aging, adhesion drops to grade 3. Third, the resin system's crosslinking network cannot simultaneously achieve rigidity and toughness, resulting in a pencil hardness of only 2H, impact strength of 30cm, and flexibility of 4mm, with mechanical properties far lower than the example. Finally, this system does not incorporate MAP-POSS cage-type reinforcement structures and La... 3+The bridging one-dimensional-two-dimensional hybrid nano-reinforced phase cannot construct a dense cross-linked network and a disordered network structure that blocks corrosion. After 1000 hours of neutral salt spray, edge blistering and rust appear. After 100 cycles of hot and cold cycling, local cracking and peeling occur. The long-term service stability is extremely poor and cannot meet the high-performance requirements of automotive sheet metal repair.

[0125] In Comparative Example 2, MAP-POSS was removed and replaced with styrene during the preparation of photosensitive resin A, while the nano-reinforcing phase was replaced with an equal amount of fumed silica. Firstly, MAP-POSS contains photopolymerizable methacryloyloxy groups, which can chemically bond to the resin crosslinking network, increasing crosslinking density and free radical utilization efficiency. Removing MAP-POSS significantly reduced the crosslinking activity of the resin system, resulting in severely insufficient deep curing ability for thick coatings. The curing degree of the 5mm thick coating was only 62.3%, far lower than the 98.2% in Example 2. Simultaneously, the curing speed was significantly slower, with a surface drying time of 60s and a complete curing time of 120s. Secondly, the nano-reinforcing phase in Example 2 was a hybrid of La³⁺-coordinated activated BNNTs / ZrP nanosheets. The original structure could form a continuous mechanical reinforcement network and corrosion barrier in the resin. However, when replaced with fumed silica, which only has a thickening effect, the system lost its nanoscale reinforcement and barrier effects. The rigidity and toughness of the resin cross-linking network were severely insufficient, resulting in a decrease in pencil hardness to H, cross-cut adhesion level to 2, impact strength to only 20 cm, and flexibility to 5 mm. The mechanical properties deteriorated across the board. Finally, the resin system lost the synergistic effect of MAP-POSS and the nano-reinforcing phase on weather resistance. Its resistance to damp heat aging, salt spray, and thermal cycling all failed severely, making it unable to meet the requirements for long-term service.

[0126] In Comparative Example 3, MAP-POSS was removed and replaced with styrene during the preparation of photosensitive resin A, while retaining the nano-reinforced phase system. First, the inorganic Si-O-Si cage structure of MAP-POSS can be covalently integrated into the three-dimensional network of the resin, improving the crosslinking density, free radical utilization efficiency, and thick coating curing ability. After removal, the crosslinking density of the resin system decreases, the photocuring reaction rate slows down, the surface drying time increases to 45s, the complete curing time increases to 80s, and the curing degree of the 5mm thick coating substrate decreases to 88.5%. Second, without the rigidity enhancement and weather resistance modification effect of the MAP-POSS cage structure on the resin matrix, the mechanical properties and environmental stability of the resin crosslinking network decrease, the pencil hardness decreases to H, the cross-cut adhesion is grade 1, the impact strength is 35cm, and the flexibility is 3mm. Finally, although the nano-reinforcing phase is retained in Comparative Example 3, it can still provide certain mechanical reinforcement and barrier effects, and its performance is better than that of Comparative Example 2, which removes both MAP-POSS and the nano-reinforcing phase. However, it cannot achieve the synergistic modification of MAP-POSS and the nano-reinforcing phase, and its resistance to damp heat, salt spray, and thermal cycling is still significantly lower than that of Example 2.

[0127] In Comparative Example 4, the nano-reinforcing phase was replaced with an equal amount of activated BNNTs and ZrP nanosheets in a 1:1 physical composite, and La was eliminated. 3+ Hybridization process of coordination bridging. First, in Example 2, La... 3+ The coordination effect of the nanofiller can form stable coordination bonds with the active hydroxyl groups on the surface of activated BNNTs and ZrP nanosheets, constructing a one-dimensional-two-dimensional hybrid three-dimensional nanostructure. This avoids the entanglement and aggregation of nanotubes and the stacking and aggregation of nanosheets, improving the dispersibility of the filler in the resin, and also achieving efficient stress transfer and barrier against corrosive media. In contrast, the physically compounded nanofiller in Comparative Example 4 lacks coordination bridging effect, is prone to self-aggregation, has poor dispersion uniformity in the resin, and cannot form a continuous reinforcing and barrier network. Furthermore, the interfacial bonding force between the nanofiller and the resin matrix is ​​significantly reduced, and interfacial debonding easily occurs under stress, forming stress concentration points, resulting in significant deterioration of mechanical properties, with a pencil hardness of only 2H, cross-cut adhesion grade 1, impact strength of 38cm, and flexibility of 3mm. Finally, the agglomerated nanofiller cannot form a dense, disordered network barrier structure, and corrosive media can easily penetrate rapidly through the defects formed by the agglomerates. Its resistance to damp heat aging, salt spray, and thermal cycling is significantly lower than that of Example 2.

[0128] In Comparative Example 5, the nano-reinforcing phase was replaced with an equal amount of talc, completely eliminating the hybrid nano-reinforcing phase system of Example 2. On the one hand, talc is a conventional micron-level filler that can only fill volume and cannot provide nano-level mechanical reinforcement. The one-dimensional-two-dimensional hybrid nano-reinforcing phase in Example 2 can dissipate impact energy through crack bridging and crack deflection effects, significantly improving the mechanical properties of the system. After being replaced with talc, the system loses its nano-reinforcing effect, and the mechanical properties decline across the board, with pencil hardness dropping to H, cross-cut adhesion grade 1, impact strength 32cm, and flexibility 4mm. On the other hand, talc cannot form a disordered network barrier that combines lamellar and tubular structures, significantly shortening the penetration path of corrosive media. The putty's resistance to humid heat aging, neutral salt spray, and thermal cycling performance are all significantly deteriorated, and its long-term service stability is far lower than that of Example 2.

[0129] In Comparative Example 6, La was eliminated during the preparation of the nano-reinforced phase. 3+ The coordination bridging step retains only the physical mixture of activated BNNTs and ZrP nanosheets. On the one hand, La 3+ With empty f orbitals, it can form coordination bonds with active hydroxyl groups on the surfaces of two types of nanomaterials, achieving bridging hybridization between one-dimensional and two-dimensional nanomaterials, thereby constructing a stable three-dimensional nanonetwork. In Comparative Example 6, La was removed... 3+After the coordination step, the activated BNNTs and ZrP nanosheets are simply mixed physically, which easily leads to entanglement and stacking agglomeration. The dispersion in the resin matrix is ​​extremely poor, and it is impossible to form a continuous mechanical reinforcement and barrier network. Furthermore, the interfacial bonding force between the nanofiller and the resin matrix decreases significantly, the stress transfer efficiency decreases, and the mechanical properties of the putty deteriorate significantly. The pencil hardness drops to H, the cross-cut adhesion is grade 2, the impact strength is 33cm, and the flexibility is 4mm. On the other hand, the agglomerated nanofiller will form a large number of defects in the system, and corrosive media can easily penetrate through the defects. The resistance to damp heat, salt spray, and thermal cycling is far lower than that of Example 2.

[0130] In Comparative Example 7, the ZrP nanosheet component was removed during the preparation of the nano-reinforced phase, retaining only activated BNNTs and La. 3+ The system is as follows: On the one hand, the nano-reinforcing phase in Example 2 relies on the synergistic effect of two-dimensional ZrP nanosheets and one-dimensional activated BNNTs to construct a three-dimensional network. ZrP nanosheets have an ultra-high aspect ratio, which can provide lamellar support sites, avoid the entanglement and aggregation of activated BNNTs, and at the same time form a maze effect to extend the penetration path of corrosive media. After removing ZrP nanosheets, the remaining one-dimensional activated BNNTs are prone to self-entanglement and aggregation, and cannot form a uniformly dispersed three-dimensional network, thus losing the barrier effect of the lamellar structure. Furthermore, the resin system loses the synergistic mechanical reinforcement effect of the one-dimensional and two-dimensional structure, and cannot achieve the synergy of crack bridging and crack deflection, resulting in a significant decrease in mechanical properties, with pencil hardness reduced to H, cross-cut adhesion grade 2, impact strength 31 cm, and flexibility 4 mm. On the other hand, without the lamellar barrier effect of ZrP nanosheets, the penetration path of corrosive media is greatly shortened, and the resistance to damp heat, salt spray, and thermal cycling performance are all significantly deteriorated.

[0131] In Comparative Example 8, the activated BNNTs component was removed during the preparation of the nano-reinforced phase, retaining only ZrP nanosheets and La. 3+ The system. On the one hand, in the nano-reinforcing phase of Example 2, activated BNNTs, as a one-dimensional nano-reinforcing phase, can play a bridging role in the resin system, effectively bridging microcracks in the resin matrix and dissipating impact energy. At the same time, it provides overlapping sites for ZrP nanosheets, avoiding the stacking and aggregation of nanosheets. After removing activated BNNTs, the remaining two-dimensional ZrP nanosheets are prone to lamellar stacking and cannot form a continuous three-dimensional reinforcing network, thus losing the crack bridging effect of one-dimensional nanotubes. Furthermore, the resin system loses the synergistic mechanical reinforcement effect of the one-dimensional and two-dimensional structures, and the mechanical properties are comprehensively reduced, with pencil hardness dropping to H, cross-cut adhesion grade 2, impact strength 32cm, and flexibility 4mm. On the other hand, the stacked ZrP nanosheets cannot form a dense, disordered network barrier structure, and corrosive media can easily penetrate rapidly through the gaps between the lamellar layers, resulting in significant deterioration in resistance to damp heat, salt spray, and thermal cycling.

[0132] In summary, this application provides a light-curing quick-repair putty and its preparation method. This putty uses a functionalized modified resin as its core, combined with a MAP-POSS grafted modified photosensitive resin system and La... 3+ A three-dimensional hybrid nano-reinforcing phase, composed of coordination-bridged one-dimensional activated BNNTs and two-dimensional ZrP nanosheets, is prepared by dispersion, degassing, and ball milling processes, in conjunction with a photoinitiator, additives, and fillers. This application significantly improves the photocuring performance and substrate adhesion of the putty through resin molecular structure design, significantly increases the curing speed of the putty, and extends its service life. Through MAP-POSS organic-inorganic hybrid modification, the complete curing degree of the putty during thick coating is significantly improved. Furthermore, the rare-earth coordination-bridged three-dimensional hybrid nano-reinforcing phase achieves a simultaneous leap in both the material's mechanical properties and long-term protective performance. The light-curing quick-repair putty of this application can achieve surface drying in 25 seconds and complete curing in 40 seconds. The curing degree of a 5mm thick base coat reaches 98.2%. It also has a 3H pencil hardness, 0-level adhesion, 55cm impact strength and 1mm flexibility. It still maintains excellent performance after 1000h of damp heat aging, 1000h of neutral salt spray and 100 cycles of hot and cold. It is superior to mainstream products on the market and can be widely used in the rapid repair of automotive sheet metal. It has the advantages of controllable preparation process, high construction efficiency, excellent comprehensive performance and easy promotion and implementation.

[0133] The embodiments provided by the present invention have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of the present invention. The descriptions of the embodiments above are merely for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A light-curing quick-repair putty, characterized in that, By weight, it consists of the following components: Photosensitive resin A 320-400 parts, photoinitiator 6-9 parts, dispersant 5-7 parts, defoamer 1-2 parts, leveling agent 0.5-1.5 parts, filler 330-397 parts, accelerator 2-4 parts, and ultraviolet absorber 0.5-1 part; The filler, by weight, comprises the following components: Titanium dioxide 2.2-2.5 parts, fumed silica 5-9 parts, talc 310-365 parts, nano-reinforcing phase 14-19 parts, lanthanum chloride 1-1.5 parts; The photosensitive resin A is obtained by grafting a functionalized modified resin matrix with methacryloxypropyl cage-type silsesquioxane. The functionalized modified resin matrix is ​​obtained by polymerizing allyl ether, phosphate ester, polyol, and polyacid. The nano-reinforcing phase is a lanthanum-coordinated bridging multidimensional modified nanocomposite.

2. The light-curing quick-repair putty according to claim 1, characterized in that, The preparation method of the photosensitive resin A includes the following steps: Step 101. Add the functionalized modified resin matrix, styrene, TBHQ and MAP-POSS into the dilution vessel in a predetermined ratio. React at 80℃, nitrogen flow rate of 50mL / min and 100rpm-150rpm for 2 hours. Then, cool the reaction system to 50℃ and keep it at that temperature to obtain the crude grafted modified resin. Step 102. Add 1,4-naphthoquinone, antioxidant 1010, antioxidant 168 and TBHQ into a dilution vessel in a predetermined ratio. Stir for 40 minutes at 45°C, nitrogen flow rate of 15 mL / min and 100-150 rpm to obtain photosensitive resin A.

3. The light-curing quick-repair putty according to claim 2, characterized in that, The method for preparing the functionalized modified resin matrix includes the following steps: Step 201. Ethylene glycol, neopentyl glycol, tetrahydrophthalic anhydride, and TBHQ are added to a reaction vessel in a predetermined ratio. The mixture is reacted at 0.02 MPa, nitrogen flow rate of 50 mL / min, 200 rpm-300 rpm, and 160 °C for 1 hour to obtain a molten material. The molten material is then reacted at 210 °C, -0.095 MPa, and under oil-water separation conditions for 3 hours to obtain a primary esterified polycondensate. Step 202. Cool the primary esterified condensate obtained in step 201 to 90°C, and add maleic anhydride in a predetermined ratio to the primary esterified condensate. React for 4 hours under the conditions of 0.02 MPa, 210°C, and 200 rpm-300 rpm to obtain the secondary esterified condensate. Step 203. Cool the secondary esterified condensate obtained in step 202 to 165°C, and add the pre-prepared ratio of trimethylolpropane diallyl ether and hydroxyethyl methacrylate phosphate to the reaction system. After reacting for 3 hours at 140°C and 150-250 rpm, the functionalized modified resin matrix is ​​obtained.

4. The light-curing quick-repair putty according to claim 3, characterized in that, In step 201, the top temperature of the distillation column is ≤102℃, and the acid value is measured once every 1 hour until the acid value is 25mgKOH / g-28mgKOH / g; In step 202, the acid value is sampled and tested every 1 hour until the acid value stabilizes at 40mgKOH / g-50mgKOH / g; In step 203, samples are taken every 1 hour to test the acid value and viscosity. When the acid value stabilizes at 20mgKOH / g-25mgKOH / g and is diluted with solvent to a solid content of 50%, the viscosity is measured at 25°C using a cone-plate viscometer at a value of 620mPa・s-680mPa・s. At this point, heating is stopped and rapid cooling is initiated.

5. The light-curing quick-repair putty according to claim 1, characterized in that, The preparation method of the nano-reinforced phase includes the following steps: Step 301. ZrP nanosheets and deionized water are sequentially added to an ultrasonic reactor and ultrasonicated for 30 minutes under ultrasonic power of 300W and ice bath temperature of 5℃ to obtain ZrP colloid. Step 302. Activated BNNTs and deionized water are added sequentially into an ultrasonic reactor. After ultrasonication for 30 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, activated BNNTs colloid is obtained. Then, the ZrP colloid prepared in step 301 is added into the activated BNNTs colloid. After ultrasonication for 10 minutes at an ultrasonic power of 300W and an ice bath temperature of 5°C, a composite colloid is obtained. Step 303. The composite colloid prepared in step 302 and the 1.25wt% lanthanum chloride solution are added to a stirred tank in a mass ratio of 400:

1. The mixture is stirred at room temperature and 500 rpm for 30 min to obtain the composite reaction solution. Step 304. After centrifuging the composite reaction solution obtained in step 303, collect the precipitate and wash it three times alternately with deionized water and anhydrous ethanol. After washing, the precipitate is vacuum dried at 60℃ and gauge pressure -0.095MPa for 12 hours, ground in an agate mortar and passed through an 800-mesh standard sieve to obtain the nano-reinforced phase.

6. The light-curing quick-repair putty according to claim 5, characterized in that, The preparation method of activated BNNTs includes the following steps: The pre-mixed boron nitride nanotube powder was spread evenly on a quartz sample stage and placed in the discharge chamber of a cold plasma treatment instrument. The chamber was closed and evacuated to an absolute pressure ≤10 Pa and held for 10 min. Pure oxygen was introduced until the chamber pressure stabilized at 30 Pa and the oxygen flow rate was 10 mL / min. The discharge power was set to 100 W, and each treatment lasted 2 min, for a total of 3 treatments. After all treatments were completed, the samples were vacuum dried at 60 °C and a gauge pressure of -0.095 MPa for 12 h to obtain activated BNNTs.

7. The light-curing quick-repair putty according to claim 5, characterized in that, The preparation method of ZrP nanosheets includes the following steps: Step 401. Add α-zirconium phosphate powder and deionized water to the reaction vessel in sequence, and stir for 40 minutes at room temperature and 500 rpm to obtain the emulsion system. Step 402. Add tetrabutylammonium hydroxide solution dropwise to the emulsion system, stir for 12 hours under ice bath conditions of 0℃ and 400 rpm, and then sonicate for 1 hour under ultrasonic power of 300W and ice bath conditions of 10℃ to obtain a transparent system. Step 403. After centrifuging the transparent system prepared in step 402, take the supernatant and add dilute hydrochloric acid to it to obtain a white flocculent precipitate; after centrifuging the precipitate and removing the supernatant, wash and vacuum dry it to obtain ZrP nanosheets.

8. The light-curing quick-repair putty according to claim 7, characterized in that, In step 402, the concentration of tetrabutylammonium hydroxide is 0.1 mol / L.

9. The light-curing quick-repair putty according to claim 7, characterized in that, In step 402, the molar ratio of α-zirconium phosphate and tetrabutylammonium hydroxide is controlled to be 2:

1.

10. A method for preparing a light-curing quick-repair putty, characterized in that, The method for preparing the light-curing quick-repair putty according to any one of claims 1-9 comprises the following steps: Step 501. Add the pre-mixed photosensitive resin A into a stirred tank and disperse it for 10 minutes at 25℃-30℃ and 1200rpm to obtain the liquid phase body. Then add the pre-mixed dispersant, defoamer, leveling agent, accelerator, ultraviolet absorber, photoinitiator, and nano-reinforcing phase into the liquid phase body in one go. Stir for 30 minutes at 15℃ in a water bath, in the dark, and at 1800rpm to obtain the premixed resin liquid. Step 502. Add fumed silica, rutile titanium dioxide, talc and lanthanum chloride to the premixed resin liquid prepared in step 501 in a preset ratio. After dispersing at room temperature and 2800rpm-3000rpm for 45min, a coarse dispersion slurry is obtained. Step 503. Transfer the coarse dispersion slurry prepared in step 502 to a vacuum degassing machine, stir for 20 minutes under the conditions of constant temperature of 25℃, -0.09MPa, and 1200rpm in a water bath, and then break the vacuum to obtain a fine dispersion slurry; then transfer the fine dispersion slurry to a horizontal ball mill and ball mill until the slurry fineness is ≤20μm to obtain a light-curing quick-repair putty.

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