Preparation process of high-viscosity anti-ultraviolet glue

Abstract

The invention relates to the technical field of adhesives, in particular to a preparation process of high-viscosity anti-ultraviolet glue. Comprising the following steps: preparing anti-ultraviolet composite particles; preparing a high-dispersion permeation solvent; copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate; and compounding of glue. Graphite-phase carbon nitride is calcined and added into a sodium humate solution for ultrasonic dispersion, pH is adjusted to obtain humic acid / carbon nitride composite powder, when graphite-phase carbon nitride is irradiated by ultraviolet light, the graphite-phase carbon nitride absorbs energy of ultraviolet light to generate a large number of. OH and. O2-free radicals, at the moment, a humic acid film can quench and remove the free radicals, and therefore the carbon nitride / humic acid composite powder is obtained. According to the preparation method of the anti-ultraviolet composite particles, photo-generated carriers are consumed, so that the ultraviolet absorption capacity of secondary calcined graphite phase carbon nitride is synergistically enhanced, and when the prepared anti-ultraviolet composite particles are ultrasonically dispersed in high-viscosity anti-ultraviolet glue, the anti-ultraviolet performance of the glue can be effectively enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, in particular to a preparation process of high-viscosity UV-resistant glue. Background Art

[0002] Polyvinyl chloride (PVC) is a widely used material. Due to its excellent corrosion resistance and certain mechanical strength, it is widely used in daily products and chemical anti-corrosion fields. For example, PVC pipes are used as new applications in drainage and sewage treatment. However, the current pressure-bearing capacity of PVC pipes is relatively low. In addition, improper construction methods or poor coordination between pipes and fittings often lead to leakage or seepage in the completed PVC pipelines. At this time, it is necessary to remove the leaking part and reinstall it or use adhesives for anti-leakage treatment. The former is time-consuming and labor-intensive and has a large economic loss, while the latter has the characteristics of convenient construction. Therefore, the development of high-quality adhesives is particularly important.

[0003] Commonly used adhesives include acrylic adhesives, polyvinyl acetate adhesives and polyurethane adhesives. The surface of PVC pipes is smooth. Although conventional acrylic and polyvinyl acetate adhesives have low volatile content, are safe and non-toxic, their adhesion to PVC materials is poor. Polyurethane adhesives are used because of their good wettability and high initial bonding strength, but they are prone to lose their bonding properties under harsh conditions such as long-term ultraviolet radiation. At the same time, PVC pipes are often exposed to outdoor environments. Long-term exposure to ultraviolet rays will cause glue aging and reduce bonding strength, which will in turn affect the sealing and durability of the pipeline system. Summary of the invention

[0004] In order to solve the above technical defects, the present invention has developed a preparation process of high-viscosity anti-UV glue. The prepared high-viscosity anti-UV glue has excellent bonding performance and anti-UV ability, and can well repair and bond PVC pipes and maintain stability.

[0005] A preparation process of high-viscosity UV-resistant glue comprises the following steps:

[0006] S1: Preparation of UV-resistant composite particles

[0007] The graphite phase carbon nitride powder is subjected to secondary calcination to obtain secondary calcined graphite phase carbon nitride, sodium humate is dissolved in deionized water, and then the secondary calcined graphite phase carbon nitride is added for ultrasonic treatment, pH is adjusted, stirring and centrifuging are performed, and the humic acid / carbon nitride composite powder is obtained, epoxy resin is dissolved in a mixed solvent of n-butanol and xylene, and then the humic acid / carbon nitride composite powder is added to perform a temperature rise reflux reaction, and the mixture is washed clean after centrifugation and air-dried to obtain anti-ultraviolet composite particles;

[0008] S2: Preparation of highly dispersed penetrating solvent

[0009] The butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether are mixed uniformly in a nitrogen atmosphere, a silane coupling agent is added, the temperature is raised for reflux reaction, magnesium silicate is added, stirred and filtered to obtain a polyether penetration liquid, 1,2-dichloroethane, polyacrylate, tetrahydrofuran and the polyether penetration liquid are mixed uniformly in a nitrogen atmosphere, dibutyltin dioxysilicate and UV powder are added and stirred to obtain a highly dispersed penetration solvent;

[0010] S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue

[0011] Dibenzoyl peroxide is dissolved in a mixed system of 2-ethylhexyl acrylate and 1,2-dichloroethane, chlorinated polyvinyl chloride powder is added in a nitrogen atmosphere to dissolve, and then the temperature is raised and stirred for reaction, anhydrous ethanol is added and centrifuged and filtered, and then the mixture is cleaned and dried to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer, which is dissolved in a highly dispersed penetrating solvent, and then anti-ultraviolet composite particles are added for high-speed mixing to obtain a high-viscosity anti-ultraviolet glue.

[0012] Furthermore, step S1 of preparing the anti-ultraviolet composite particles comprises the following steps:

[0013] S1.1: Spread the graphite phase carbon nitride powder evenly in a ceramic combustion boat, then put it in a tube furnace, raise the temperature in the tube furnace to 525-550°C at a heating rate of 4-6°C / min in an air atmosphere, then keep it warm for 1-1.2 hours to calcine, cool it down with the furnace to obtain the primary calcined graphite phase carbon nitride, spread the primary calcined graphite phase carbon nitride in the ceramic combustion boat evenly, then continue to place it in a tube furnace and heat it to 550-575°C at a heating rate of 2-2.5°C / min, keep it warm for 1-1.5 hours to calcine, then cool it down with the furnace to obtain the secondary calcined graphite phase carbon nitride;

[0014] S1.2: 0.6-0.8 parts by weight of sodium humate and 120-150 parts by weight of deionized water are mixed and added to a container, and stirred until the sodium humate is completely dissolved to obtain a sodium humate solution. 3-4 parts by weight of secondary calcined graphite phase carbon nitride are added to the sodium humate solution, and then placed in an ultrasonic disperser for ultrasonic treatment at an ultrasonic frequency of 25-30kHz for 8-10 minutes, and then 0.1-0.2 mol / L sulfuric acid solution is added to adjust the pH to 2-3, and stirred at a stirring speed of 180-200 rpm for 12-15 minutes, and then centrifuged at a speed of 8000-8500 rpm for 5-6 minutes to separate solid particles, rinsed with deionized water 2-3 times and dried to obtain a humic acid / carbon nitride composite powder;

[0015] S1.3: Place 6-8 parts by weight of n-butanol and 14-18 parts by weight of xylene in a flask with a reflux device, stir at a stirring speed of 200-250rpm for 15-20 minutes, then add 5-6 parts by weight of epoxy resin, heat to 70-75°C and stir until the epoxy resin is fully dissolved, then add 30-35 parts by weight of humic acid / carbon nitride composite powder, heat to 130-140°C for reflux reaction, continue for 6-6.5 hours, cool, add 3-5 times the volume of acetone for centrifugal washing, repeat 2-3 times, rinse with deionized water, and dry to obtain anti-ultraviolet composite particles.

[0016] Furthermore, the preparation of the highly dispersed penetrating solvent in step S2 comprises the following steps:

[0017] S2.1: Add butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether into a reactor in a mass ratio of 1: (40-45): (110-115), continue to introduce nitrogen into the reactor to exhaust the air, then continue to stir at a stirring rate of 60-80 rpm, add 12-15 wt% of silane coupling agent, heat to 55-60° C. for 1.5-2 hours of reflux reaction, then heat to 80-85° C., react for 2-3 hours, cool to room temperature, add magnesium silicate and stir for 15-20 minutes, filter and collect the filtrate to obtain a polyether permeate;

[0018] S2.2: Add 6-8 parts by weight of 1,2-dichloroethane, 0.8-1 parts by weight of polyacrylate, 1-1.5 parts by weight of tetrahydrofuran and 0.4-0.6 parts by weight of polyether penetrant into a reaction kettle, continue to introduce nitrogen to exhaust the air in the kettle, then stir at a stirring rate of 50-60rpm for 20-25 minutes, add 0.03-0.05wt% of dibutyltin disilicate and 1-2wt% of UV powder, continue to stir at a stirring rate of 50-60rpm for 20-25 minutes to obtain a highly dispersed penetrant solvent.

[0019] Furthermore, step S3 of copolymerizing chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding glue comprises the following steps:

[0020] S3.1: 2-ethylhexyl acrylate and 1,2-dichloroethane are placed in a container at a mass ratio of 1:(1.5-2), 1-1.5wt% of dibenzoyl peroxide is added, and the mixture is stirred with a glass rod until the dibenzoyl peroxide is completely dissolved, and then the mixture is transferred to a flask, and nitrogen is continuously introduced for 8-10 minutes, and then 20-30wt% of chlorinated polyvinyl chloride powder is added, and the nitrogen is stopped after stirring until the chlorinated polyvinyl chloride is completely dissolved. The three-necked flask is connected to a condenser and heated and stirred at a temperature of 80-85°C and a stirring rate of 60-80rpm for 2-2.5 hours, and 1-1.5 times the volume of anhydrous ethanol is added to mix evenly, and then the precipitate is collected by centrifugal filtration, rinsed with deionized water, and dried to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer;

[0021] S3.2: Add 10-15 parts by weight of highly dispersed penetrating solvent into a container, then place the container on a magnetic stirrer, add a rotor and continue stirring at a stirring speed of 180-200rpm, then slowly add 2-3 parts by weight of chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer and 0.1-0.2 parts by weight, heat to 55-60°C until the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer is completely dissolved, then add 0.6-0.8 parts by weight of anti-UV composite particles, transfer to a high-speed mixer and mix at a speed of 3000-3500rpm for 15-20 minutes to obtain a high-viscosity anti-UV glue.

[0022] Furthermore, in step S1.2, the particle size of the graphite phase carbon nitride powder is 500-1000 nm.

[0023] Furthermore, the epoxy resin in step S1.3 is bisphenol A epoxy resin with a molecular weight of 4000-4500.

[0024] Furthermore, the silane coupling agent in step S2.1 is γ-glycidyloxypropyltrimethoxysilane.

[0025] Furthermore, the UV powder in step S2.2 is bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate.

[0026] Furthermore, in step S3.1, the drying temperature of the chlorinated polyvinyl chloride / poly(2-ethylhexyl acrylate) copolymer is 50-55°C.

[0027] Furthermore, in step S3.2, the chlorinated polyvinyl chloride / poly(2-ethylhexyl acrylate) copolymer is slowly added within 25-30 minutes.

[0028] The beneficial effects are as follows: 1. The present invention performs secondary calcination on graphite phase carbon nitride powder to form secondary calcined graphite phase carbon nitride with mesopores and wider band gap, which has high specific surface area and good ultraviolet absorption ability, and then prepares sodium humate solution, adds the secondary calcined graphite phase carbon nitride for ultrasonic dispersion, adjusts the pH to be acidic so that sodium humate generates humic acid and precipitates, thereby attaching a layer of humic acid film on the surface and interlayer of the secondary calcined graphite phase carbon nitride to obtain humic acid / carbon nitride composite powder. Humic acid can absorb ultraviolet rays in a wide wavelength range, and act as an effective free radical quencher or inhibit the photochemical reaction process through light shielding effect. When the graphite phase carbon nitride is irradiated by ultraviolet rays, it absorbs the energy of ultraviolet light to generate a large amount of ·OH and ·O 2 - Free radicals, at this time the humic acid film can quench and remove these free radicals, consume photogenerated carriers, thereby synergistically enhancing the ultraviolet absorption capacity of the secondary calcined graphite phase carbon nitride. The prepared anti-ultraviolet composite particles can effectively enhance the anti-ultraviolet performance of the glue when ultrasonically dispersed in high-viscosity anti-ultraviolet glue.

[0029] 2. The present invention dissolves the epoxy resin in a mixed solvent of n-butanol and xylene, and then adds humic acid / carbon nitride composite powder to carry out a temperature-raising reflux reaction. At this time, the surface of the humic acid / carbon nitride composite powder can provide a large number of hydroxyl groups as active sites, which undergo a ring-opening reaction with the epoxy groups in the epoxy resin chain, thereby grafting the epoxy molecules to the surface of the humic acid / carbon nitride composite powder, which can greatly improve the dispersibility of the anti-ultraviolet composite particles in the subsequent high-dispersion penetrating solvent and improve the bonding strength of the glue.

[0030] 3. The present invention prepares a polyether penetrant by subjecting an antioxidant butylhydroxytoluene, toluene, a silane coupling agent and hydroxyalkylphenol polyoxyethylene ether to a reflux reaction in a nitrogen atmosphere, and then mixes the polyether penetrant with 1,2-dichloroethane, polyacrylate and tetrahydrofuran to prepare a highly dispersed penetrant solvent. As a colloid solvent, the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl ester copolymer can be better dissolved therein, and the tetrahydrofuran and polyether components can interact with the matrix of polar and non-polar molecules to swell the surface molecular chains, thereby carrying the colloid to penetrate the bonding matrix, forming glue nails inside the bonding matrix, and greatly enhancing the bonding ability and application range of the colloid.

[0031] 4. The present invention obtains a chlorinated polyvinyl chloride / poly(2-ethylhexyl acrylic acid) copolymer by blending 2-ethylhexyl acrylate and chlorinated polyvinyl chloride, and then performing in-situ polymerization of the blending under the action of a dibenzoyl peroxide initiator. The chlorinated polyvinyl chloride and poly(2-ethylhexyl acrylic acid) form interpenetration of two-phase polymers at the interface, and the obtained copolymer has a good bonding effect, thereby improving the bonding strength of the glue. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The present invention is a flow chart of the preparation process of the high-viscosity UV-resistant glue used in the embodiments of the present invention. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] A preparation process of high viscosity UV-resistant glue, such as Figure 1 As shown, the following steps are included:

[0036] S1: Preparation of UV-resistant composite particles

[0037] S1.1: Spread the graphite phase carbon nitride powder with a particle size of 500nm evenly in a ceramic combustion boat, and then put it into a tube furnace, raise the temperature in the tube furnace to 525℃ at a heating rate of 4℃ / min in an air atmosphere, and then keep it warm for 1 hour to calcine, and then cool it down with the furnace to obtain the primary calcined graphite phase carbon nitride, spread the primary calcined graphite phase carbon nitride in the ceramic combustion boat, and then continue to place it in a tube furnace and heat it to 550℃ at a heating rate of 2℃ / min, keep it warm for 1 hour to calcine, and then cool it down with the furnace to obtain the secondary calcined graphite phase carbon nitride;

[0038] S1.2: 0.6 parts by weight of sodium humate and 120 parts by weight of deionized water are mixed and added to a container, and stirred until the sodium humate is completely dissolved to obtain a sodium humate solution. 3 parts by weight of secondary calcined graphite phase carbon nitride are added to the sodium humate solution, and then placed in an ultrasonic disperser for ultrasonic treatment at an ultrasonic frequency of 25 kHz for 8 minutes, and then 0.1 mol / L sulfuric acid solution is added to adjust the pH to 3, and stirred at a stirring speed of 180 rpm for 12 minutes, and then centrifuged at a speed of 8000 rpm for 5 minutes to separate solid particles, rinsed twice with deionized water and dried to obtain a humic acid / carbon nitride composite powder;

[0039] S1.3: Place 6 parts by weight of n-butanol and 14 parts by weight of xylene in a flask with a reflux device, stir at a stirring speed of 200 rpm for 15 minutes, then add 5 parts by weight of bisphenol A epoxy resin with a molecular weight of 4000, heat to 70°C and stir until the epoxy resin is fully dissolved, then add 30 parts by weight of humic acid / carbon nitride composite powder, heat to 130°C for reflux reaction, continue for 6 hours, cool, add 3 times the volume of acetone for centrifugal washing, repeat 2 times, rinse with deionized water, and dry to obtain anti-UV composite particles.

[0040] S2: Preparation of highly dispersed penetrating solvent

[0041] S2.1: Add butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether into a reactor in a mass ratio of 1:40:110, continue to introduce nitrogen into the reactor to exhaust the air, then continue to stir at a stirring rate of 60 rpm, add 12 wt % of γ-glycidyloxypropyltrimethoxysilane, heat to 55° C. for 1.5 hours of reflux reaction, then heat to 80° C. for 2 hours, cool to room temperature, add magnesium silicate and stir for 15 minutes, filter and collect the filtrate to obtain a polyether permeate;

[0042] S2.2: Add 6 parts by weight of 1,2-dichloroethane, 0.8 parts by weight of polyacrylate, 1 part by weight of tetrahydrofuran and 0.4 parts by weight of polyether penetrant into a reaction kettle, continue to introduce nitrogen to exhaust the air in the kettle, then stir at a stirring rate of 50 rpm for 20 minutes, add 0.03 wt% of dibutyltin disilicate and 1 wt% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, continue stirring at a stirring rate of 50 rpm for 20 minutes to obtain a highly dispersed penetrant solvent.

[0043] S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue

[0044] S3.1: 2-Ethylhexyl acrylate and 1,2-dichloroethane are placed in a container at a mass ratio of 1:1.5, 1 wt% of dibenzoyl peroxide is added, and the mixture is stirred with a glass rod until the dibenzoyl peroxide is completely dissolved, then the mixture is transferred to a flask, and nitrogen is continuously introduced for 8 minutes, and then 20 wt% of chlorinated polyvinyl chloride powder is added, and the nitrogen is stopped after stirring until the chlorinated polyvinyl chloride is completely dissolved. The three-necked flask is connected to a condenser and heated and stirred at a temperature of 80°C and a stirring rate of 60 rpm for 2 hours, and 1 volume of anhydrous ethanol is added and mixed evenly, and then the precipitate is collected by centrifugal filtration, rinsed with deionized water, and dried at 50°C to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer;

[0045] S3.2: Add 10 parts by weight of highly dispersed penetrating solvent into a container, then place the container on a magnetic stirrer, add a rotor and continue stirring at a stirring speed of 180 rpm, then add 2 parts by weight of chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer within 25 minutes, heat to 55°C until the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer is completely dissolved, then add 0.6 parts by weight of anti-UV composite particles, transfer to a high-speed mixer and mix at a speed of 3000 rpm for 15 minutes to obtain a high-viscosity anti-UV glue.

[0046] Example 2

[0047] A preparation process of high viscosity UV-resistant glue, such as Figure 1 As shown, the following steps are included:

[0048] S1: Preparation of UV-resistant composite particles

[0049] S1.1: Spread the graphite phase carbon nitride powder with a particle size of 500nm evenly in a ceramic combustion boat, and then put it into a tube furnace, raise the temperature in the tube furnace to 525℃ at a heating rate of 4℃ / min in an air atmosphere, and then keep it warm for 1 hour to calcine, and then cool it down with the furnace to obtain the primary calcined graphite phase carbon nitride, spread the primary calcined graphite phase carbon nitride in the ceramic combustion boat, and then continue to place it in a tube furnace and heat it to 550℃ at a heating rate of 2℃ / min, keep it warm for 1 hour to calcine, and then cool it down with the furnace to obtain the secondary calcined graphite phase carbon nitride;

[0050] S1.2: 0.8 parts by weight of sodium humate and 150 parts by weight of deionized water are mixed and added to a container, and stirred until the sodium humate is completely dissolved to obtain a sodium humate solution. 4 parts by weight of secondary calcined graphite phase carbon nitride are added to the sodium humate solution, and then placed in an ultrasonic disperser for ultrasonic treatment at an ultrasonic frequency of 25 kHz for 8 minutes, and then 0.1 mol / L sulfuric acid solution is added to adjust the pH to 3, and stirred at a stirring speed of 180 rpm for 12 minutes, and then centrifuged at a speed of 8000 rpm for 5 minutes to separate solid particles, rinsed twice with deionized water and dried to obtain a humic acid / carbon nitride composite powder;

[0051] S1.3: Place 8 parts by weight of n-butanol and 18 parts by weight of xylene in a flask with a reflux device, stir at a stirring speed of 200 rpm for 15 minutes, then add 6 parts by weight of bisphenol A epoxy resin with a molecular weight of 4000, heat to 70°C and stir until the epoxy resin is fully dissolved, then add 35 parts by weight of humic acid / carbon nitride composite powder, heat to 130°C for reflux reaction, continue for 6 hours, cool, add 3 times the volume of acetone for centrifugal washing, repeat 2 times, rinse with deionized water, and dry to obtain anti-UV composite particles.

[0052] S2: Preparation of highly dispersed penetrating solvent

[0053] S2.1: Add butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether into a reactor in a mass ratio of 1:45:115, continue to introduce nitrogen into the reactor to exhaust the air, then continue to stir at a stirring rate of 60 rpm, add 15 wt % of γ-glycidyloxypropyltrimethoxysilane, heat to 55° C. for 1.5 hours of reflux reaction, then heat to 80° C. for 2 hours, cool to room temperature, add magnesium silicate and stir for 15 minutes, filter and collect the filtrate to obtain a polyether permeate;

[0054] S2.2: Add 8 parts by weight of 1,2-dichloroethane, 1 part by weight of polyacrylate, 1.5 parts by weight of tetrahydrofuran and 0.6 parts by weight of polyether penetrant into a reaction kettle, continue to introduce nitrogen to exhaust the air in the kettle, then stir at a stirring rate of 50 rpm for 20 minutes, add 0.05 wt% of dibutyltin diosilicate and 2 wt% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, continue stirring at a stirring rate of 50 rpm for 20 minutes to obtain a highly dispersed penetrant solvent.

[0055] S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue

[0056] S3.1: 2-Ethylhexyl acrylate and 1,2-dichloroethane are placed in a container at a mass ratio of 1:2, 1.5 wt% of dibenzoyl peroxide is added, and the mixture is stirred with a glass rod until the dibenzoyl peroxide is completely dissolved, then the mixture is transferred to a flask, and nitrogen is continuously introduced for 8 minutes, and 30 wt% of chlorinated polyvinyl chloride powder is added, and the nitrogen is stopped after stirring until the chlorinated polyvinyl chloride is completely dissolved. The three-necked flask is connected to a condenser and heated and stirred at a temperature of 80°C and a stirring rate of 60 rpm for 2 hours, and 1 volume of anhydrous ethanol is added and mixed evenly, and then the precipitate is collected by centrifugal filtration, rinsed with deionized water, and dried at 50°C to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer;

[0057] S3.2: Add 15 parts by weight of highly dispersed penetrating solvent into a container, then place the container on a magnetic stirrer, add a rotor and continue stirring at a stirring speed of 180 rpm, then add 3 parts by weight of chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer within 25 minutes, heat to 55°C until the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer is completely dissolved, then add 0.8 parts by weight of anti-UV composite particles, transfer to a high-speed mixer and mix at a speed of 3000 rpm for 15 minutes to obtain a high-viscosity anti-UV glue.

[0058] Example 3

[0059] A preparation process of high viscosity UV-resistant glue, such as Figure 1 As shown, the following steps are included:

[0060] S1: Preparation of UV-resistant composite particles

[0061] S1.1: Spread the graphite phase carbon nitride powder with a particle size of 1000nm evenly in a ceramic combustion boat, and then put it into a tube furnace, raise the temperature in the tube furnace to 550℃ at a heating rate of 6℃ / min in an air atmosphere, and then keep it warm for 1.2 hours to calcine, and then cool it down with the furnace to obtain the primary calcined graphite phase carbon nitride, spread the primary calcined graphite phase carbon nitride in the ceramic combustion boat, and then continue to place it in a tube furnace and heat it to 575℃ at a heating rate of 2.5℃ / min, keep it warm for 1.5 hours to calcine, and then cool it down with the furnace to obtain the secondary calcined graphite phase carbon nitride;

[0062] S1.2: 0.6 parts by weight of sodium humate and 120 parts by weight of deionized water are mixed and added to a container, and stirred until the sodium humate is completely dissolved to obtain a sodium humate solution. 3 parts by weight of secondary calcined graphite phase carbon nitride are added to the sodium humate solution, and then placed in an ultrasonic disperser for ultrasonic treatment at an ultrasonic frequency of 30 kHz for 10 minutes, and then 0.2 mol / L sulfuric acid solution is added to adjust the pH to 2, and stirred at a stirring speed of 200 rpm for 15 minutes, and then centrifuged at a speed of 8500 rpm for 6 minutes to separate solid particles, rinsed with deionized water 3 times and dried to obtain a humic acid / carbon nitride composite powder;

[0063] S1.3: Place 6 parts by weight of n-butanol and 14 parts by weight of xylene in a flask with a reflux device, stir at a stirring speed of 250 rpm for 20 minutes, then add 5 parts by weight of bisphenol A epoxy resin with a molecular weight of 4000, heat to 75°C and stir until the epoxy resin is fully dissolved, then add 30 parts by weight of humic acid / carbon nitride composite powder, heat to 140°C for reflux reaction, continue for 6.5 hours, cool, add 5 times the volume of acetone for centrifugal washing, repeat 3 times, rinse with deionized water, and dry to obtain anti-UV composite particles.

[0064] S2: Preparation of highly dispersed penetrating solvent

[0065] S2.1: Add butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether into a reactor in a mass ratio of 1:40:110, continue to introduce nitrogen into the reactor to exhaust the air, then continue to stir at a stirring rate of 80 rpm, add 12 wt % of γ-glycidyloxypropyltrimethoxysilane, heat to 60° C. for 2 hours of reflux reaction, then heat to 85° C. for 3 hours, cool to room temperature, add magnesium silicate and stir for 20 minutes, filter and collect the filtrate to obtain a polyether permeate;

[0066] S2.2: Add 6 parts by weight of 1,2-dichloroethane, 0.8 parts by weight of polyacrylate, 1 part by weight of tetrahydrofuran and 0.4 parts by weight of polyether penetrant into a reaction kettle, continue to introduce nitrogen to exhaust the air in the kettle, then stir at a stirring rate of 60 rpm for 25 minutes, add 0.03 wt% of dibutyltin disilicate and 1 wt% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, continue stirring at a stirring rate of 60 rpm for 25 minutes to obtain a highly dispersed penetrant solvent.

[0067] S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue

[0068] S3.1: 2-Ethylhexyl acrylate and 1,2-dichloroethane are placed in a container at a mass ratio of 1:1.5, 1 wt% of dibenzoyl peroxide is added, and the mixture is stirred with a glass rod until the dibenzoyl peroxide is completely dissolved, then the mixture is transferred to a flask, and nitrogen is continuously introduced for 10 minutes, and then 20 wt% of chlorinated polyvinyl chloride powder is added, and the nitrogen is stopped after stirring until the chlorinated polyvinyl chloride is completely dissolved. The three-necked flask is connected to a condenser and heated and stirred at a temperature of 85°C and a stirring rate of 80 rpm for 2.5 hours, and 1.5 times the volume of anhydrous ethanol is added and mixed evenly, and then the precipitate is collected by centrifugal filtration, rinsed with deionized water, and dried at 55°C to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer;

[0069] S3.2: Add 10 parts by weight of highly dispersed penetrating solvent into a container, place the container on a magnetic stirrer, add a rotor and continue stirring at a stirring speed of 200 rpm, then add 2 parts by weight of chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer within 30 minutes, heat to 60°C until the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer is completely dissolved, add 0.6 parts by weight of anti-UV composite particles, transfer to a high-speed mixer and mix at a speed of 3500 rpm for 20 minutes to obtain a high-viscosity anti-UV glue.

[0070] Comparative Example 1

[0071] Compared with Example 1, the difference of Comparative Example 1 is that step S1 is removed in Comparative Example 1, and anti-ultraviolet composite particles are not added in step S3.2. The remaining steps are the same as those in Example 1. The obtained high-viscosity anti-ultraviolet glue is recorded as Comparative Example 1.

[0072] Comparative Example 2

[0073] Compared with Example 1, the difference of Comparative Example 2 is that step S1.2 is removed in Comparative Example 2, and the humic acid / carbon nitride composite powder in step 1.3 is replaced with an equal mass of secondary calcined graphite phase carbon nitride to obtain anti-UV composite particles. The remaining steps are the same as those in Example 1, and the obtained high-viscosity anti-UV glue is recorded as Comparative Example 2.

[0074] Comparative Example 3

[0075] Compared with Example 1, the difference of Comparative Example 3 is that Comparative Example 3 removes step S1.1, replaces the secondary calcined graphite phase carbon nitride in step S1.2 with silicon dioxide powder of equal mass particle size to obtain humic acid / silicon dioxide composite powder, and replaces the humic acid / carbon nitride composite powder in step S1.3 with humic acid / silicon dioxide composite powder of equal mass to obtain anti-UV composite particles. The remaining steps are the same as in Example 1, and the obtained high-viscosity anti-UV glue is recorded as Comparative Example 3.

[0076] Comparative Example 4

[0077] Compared with Example 1, the difference of Comparative Example 4 is that step S1.3 is removed in Comparative Example 4, and the anti-ultraviolet composite particles in step S3.2 are replaced with humic acid / carbon nitride composite powder of equal mass, and the remaining steps are the same as those in Example 1. The obtained high-viscosity anti-ultraviolet glue is recorded as Comparative Example 4.

[0078] Comparative Example 5

[0079] Compared with Example 1, the difference of Comparative Example 5 is that step S2 is removed in Comparative Example 5, and the highly dispersed penetrating solvent in step S3.2 is replaced with an equal mass of 1,2-dichloroethane. The remaining steps are the same as those in Example 1, and the obtained high-viscosity anti-ultraviolet glue is recorded as Comparative Example 5.

[0080] Comparative Example 6

[0081] Compared with Example 1, the difference of Comparative Example 6 is that step S3.1 is removed in Comparative Example 6, and the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer in step S3.2 is replaced with chlorinated polyvinyl chloride of equal mass, and the remaining steps are the same as those in Example 1. The obtained high-viscosity anti-ultraviolet glue is recorded as Comparative Example 6.

[0082] Experiment 1: Take the high viscosity anti-ultraviolet glue prepared in Examples 1-3 and Comparative Examples 4-6, take three portions of each, use NDJ-8S type rotational viscometer to measure the viscosity of the glue, take the average value to record the viscosity data, and then use the roller coating method to evenly brush it on the surface of two pieces of PVC (50mm×30mm), the dosage is 0.4g, and the sample is prepared. After bonding for 5 minutes under a pressure of 1.5MPa, the initial bonding strength of the sample is tested by a tensile testing machine, and another sample is taken to measure the final bonding strength of the sample after 24h. Repeat the experiment three times to take the average value, record the data and make a table, as shown in Table 1.

[0083] Table 1: Viscosity and bonding strength of high viscosity UV-resistant glue

[0084] Viscosity (mPa·s) Initial bonding strength (N / mm) Final bonding strength (N / mm) Example 1 183.6 4.37 12.89 Example 2 188.2 4.41 13.15 Example 3 179.4 4.29 12.73 Comparative Example 4 312.8 4.04 10.54 Comparative Example 5 1043.5 2.42 7.81 Comparative Example 6 142.4 2.83 8.19

[0085] It can be seen from the data of Examples 1-3 and Comparative Example 4 in Table 1 that the humic acid / carbon nitride composite powder was not mixed with the epoxy resin solution for a temperature-raising reflux reaction, and the viscosity of the obtained high-viscosity UV-resistant glue and the bonding strength of the sample were both reduced, which can prove that grafting epoxy molecules to the surface of the humic acid / carbon nitride composite powder can improve the bonding strength of the glue.

[0086] It can be seen from the data of Examples 1-3 and Comparative Example 5 in Table 1 that when a highly dispersed penetrating solvent is not prepared as the solvent of the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer, the viscosity of the obtained high-viscosity UV-resistant glue decreases and the bonding strength of the sample decreases significantly, which proves that the highly dispersed penetrating solvent can carry the colloid to penetrate the bonding matrix, form glue nails inside the bonding matrix, and greatly enhance the bonding ability of the colloid.

[0087] It can be seen from the data of Examples 1-3 and Comparative Example 6 in Table 1 that when 2-ethylhexyl acrylate and chlorinated polyvinyl chloride are not blended for in-situ polymerization, the viscosity of the obtained high-viscosity UV-resistant glue and the bonding strength of the sample are both reduced, which proves that the copolymer prepared from chlorinated polyvinyl chloride and poly(2-ethylhexyl acrylate) has a good bonding effect, thereby being able to improve the bonding strength of the glue.

[0088] Experiment 2: Take the high viscosity anti-ultraviolet glue prepared in Example 1-3 and Comparative Example 1-3, and use a roller coating method to evenly apply it on the surface of two pieces of PVC (50mm×30mm) with a dosage of 0.4g to obtain a sample. After bonding for 5 minutes under a pressure of 1.5MPa, let it stand for 24 hours, and use a tensile testing machine to test its bonding strength N1. Then, place it in a UV box for three days with an ultraviolet wavelength of 313nm, and then test its bonding strength N2. Repeat the experiment three times in parallel, take the average value and calculate the bonding strength decrease rate = (N1-N2) / N1×100%, record and make a table, as shown in Table 2.

[0089] Table 2: Decrease in bonding strength of high viscosity UV-resistant glue after UV treatment

[0090]

[0091] It can be seen from the data of Examples 1-3 and Comparative Examples 1-3 in Table 2 that the bonding strength decrease rate of the embodiments is very small, which can prove that the prepared high-viscosity UV-resistant glues all have good UV resistance, and it can be seen from Comparative Examples 1-3 that the bonding strength decrease rate of Comparative Example 1 is large, but the sum of the bonding strength decrease rates of Comparative Example 2 and Comparative Example 3 is even greater than the bonding strength decrease rate of Comparative Example 1, indicating that there is a synergistic effect between humic acid and graphite phase carbon nitride, and the prepared UV-resistant composite particles can effectively enhance the UV resistance of the glue when ultrasonically dispersed in high-viscosity UV-resistant glue.

[0092] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A process for preparing high-viscosity UV-resistant glue, characterized in that: The following steps are involved: S1: Preparation of UV-resistant composite particles The graphite phase carbon nitride powder is subjected to secondary calcination to obtain secondary calcined graphite phase carbon nitride, sodium humate is dissolved in deionized water, and then the secondary calcined graphite phase carbon nitride is added for ultrasonic treatment, pH is adjusted, stirring and centrifuging are performed, and the humic acid / carbon nitride composite powder is obtained, epoxy resin is dissolved in a mixed solvent of n-butanol and xylene, and then the humic acid / carbon nitride composite powder is added to perform a temperature rise reflux reaction, and the mixture is washed clean after centrifugation and air-dried to obtain anti-ultraviolet composite particles; S2: Preparation of highly dispersed penetrating solvent The butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether are mixed uniformly in a nitrogen atmosphere, a silane coupling agent is added, the temperature is raised for reflux reaction, magnesium silicate is added, stirred and filtered to obtain a polyether penetration liquid, 1,2-dichloroethane, polyacrylate, tetrahydrofuran and the polyether penetration liquid are mixed uniformly in a nitrogen atmosphere, dibutyltin dioxysilicate and UV powder are added and stirred to obtain a highly dispersed penetration solvent; S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue Dibenzoyl peroxide is dissolved in a mixed system of 2-ethylhexyl acrylate and 1,2-dichloroethane, chlorinated polyvinyl chloride powder is added in a nitrogen atmosphere to dissolve, and then the temperature is raised and stirred for reaction, anhydrous ethanol is added and centrifuged and filtered, and then the mixture is cleaned and dried to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer, which is dissolved in a highly dispersed penetrating solvent, and then anti-ultraviolet composite particles are added for high-speed mixing to obtain a high-viscosity anti-ultraviolet glue.

2. The preparation process of a high-viscosity UV-resistant glue according to claim 1, characterized in that: Step S1: preparing anti-ultraviolet composite particles, comprising the following steps: S1.1: Spread the graphite phase carbon nitride powder evenly in a ceramic combustion boat, then put it in a tube furnace, raise the temperature in the tube furnace to 525-550°C at a heating rate of 4-6°C / min in an air atmosphere, then keep it warm for 1-1.2 hours to calcine, cool it down with the furnace to obtain the primary calcined graphite phase carbon nitride, spread the primary calcined graphite phase carbon nitride in the ceramic combustion boat evenly, then continue to place it in a tube furnace and heat it to 550-575°C at a heating rate of 2-2.5°C / min, keep it warm for 1-1.5 hours to calcine, then cool it down with the furnace to obtain the secondary calcined graphite phase carbon nitride; S1.2: 0.6-0.8 parts by weight of sodium humate and 120-150 parts by weight of deionized water are mixed and added to a container, and stirred until the sodium humate is completely dissolved to obtain a sodium humate solution. 3-4 parts by weight of secondary calcined graphite phase carbon nitride are added to the sodium humate solution, and then placed in an ultrasonic disperser for ultrasonic treatment at an ultrasonic frequency of 25-30kHz for 8-10 minutes, and then 0.1-0.2 mol / L sulfuric acid solution is added to adjust the pH to 2-3, and stirred at a stirring speed of 180-200 rpm for 12-15 minutes, and then centrifuged at a speed of 8000-8500 rpm for 5-6 minutes to separate solid particles, rinsed with deionized water 2-3 times and dried to obtain a humic acid / carbon nitride composite powder; S1.3: Place 6-8 parts by weight of n-butanol and 14-18 parts by weight of xylene in a flask with a reflux device, stir at a stirring speed of 200-250rpm for 15-20 minutes, then add 5-6 parts by weight of epoxy resin, heat to 70-75°C and stir until the epoxy resin is fully dissolved, then add 30-35 parts by weight of humic acid / carbon nitride composite powder, heat to 130-140°C for reflux reaction, continue for 6-6.5 hours, cool, add 3-5 times the volume of acetone for centrifugal washing, repeat 2-3 times, rinse with deionized water, and dry to obtain anti-ultraviolet composite particles.

3. The preparation process of a high-viscosity UV-resistant glue according to claim 2, characterized in that: Step S2: Preparation of highly dispersed penetrating solvent, The following steps are involved: S2.1: Mix butylated hydroxytoluene, toluene and hydroxyalkylphenol polyoxyethylene ether at a ratio of 1: (40-45): The mass ratio of (110-115) is added into a reaction kettle, nitrogen is continuously introduced into the reaction kettle to exhaust the air, and then the stirring is continuously carried out at a stirring rate of 60-80 rpm, 12-15 wt% of a silane coupling agent is added, the temperature is raised to 55-60° C. for 1.5-2 hours of reflux reaction, and then the temperature is raised to 80-85° C. for 2-3 hours. After cooling to room temperature, magnesium silicate is added and stirred for 15-20 minutes, and the filtrate is filtered and collected to obtain a polyether permeate; S2.2: Add 6-8 parts by weight of 1,2-dichloroethane, 0.8-1 parts by weight of polyacrylate, 1-1.5 parts by weight of tetrahydrofuran and 0.4-0.6 parts by weight of polyether penetrant into a reaction kettle, continue to introduce nitrogen to exhaust the air in the kettle, then stir at a stirring rate of 50-60rpm for 20-25 minutes, add 0.03-0.05wt% of dibutyltin disilicate and 1-2wt% of UV powder, continue to stir at a stirring rate of 50-60rpm for 20-25 minutes to obtain a highly dispersed penetrant solvent.

4. The preparation process of a high-viscosity UV-resistant glue according to claim 3, characterized in that: Step S3: Copolymerization of chlorinated polyvinyl chloride and 2-ethylhexyl acrylate and compounding of glue, The following steps are involved: S3.1: 2-ethylhexyl acrylate and 1,2-dichloroethane are placed in a container at a mass ratio of 1:(1.5-2), 1-1.5wt% of dibenzoyl peroxide is added, and the mixture is stirred with a glass rod until the dibenzoyl peroxide is completely dissolved, and then the mixture is transferred to a flask, and nitrogen is continuously introduced for 8-10 minutes, and then 20-30wt% of chlorinated polyvinyl chloride powder is added, and the nitrogen is stopped after stirring until the chlorinated polyvinyl chloride is completely dissolved. The three-necked flask is connected to a condenser and heated and stirred at a temperature of 80-85°C and a stirring rate of 60-80rpm for 2-2.5 hours, and 1-1.5 times the volume of anhydrous ethanol is added to mix evenly, and then the precipitate is collected by centrifugal filtration, rinsed with deionized water, and dried to obtain a chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer; S3.2: Add 10-15 parts by weight of a highly dispersed penetrating solvent into a container, place the container on a magnetic stirrer, add a rotor and continue stirring at a stirring speed of 180-200 rpm, then slowly add 2-3 parts by weight of chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer, heat to 55-60°C until the chlorinated polyvinyl chloride / polyacrylate-2-ethylhexyl copolymer is completely dissolved, then add 0.6-0.8 parts by weight of anti-UV composite particles, transfer to a high-speed mixer and mix at a speed of 3000-3500 rpm for 15-20 minutes to obtain a high-viscosity anti-UV glue.

5. The preparation process of a high-viscosity UV-resistant glue according to claim 2, characterized in that: The particle size of the graphite phase carbon nitride powder in step S1.2 is 500-1000 nm.

6. The process for preparing a high-viscosity UV-resistant glue according to claim 2, characterized in that: The epoxy resin in step S1.3 is bisphenol A epoxy resin with a molecular weight of 4000-4500.

7. The process for preparing a high-viscosity UV-resistant glue according to claim 3, characterized in that: The silane coupling agent in step S2.1 is γ-glycidyloxypropyltrimethoxysilane.

8. The process for preparing a high-viscosity UV-resistant glue according to claim 3, characterized in that: The UV powder in step S2.2 is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

9. The process for preparing a high-viscosity UV-resistant glue according to claim 4, characterized in that: The drying temperature of the chlorinated polyvinyl chloride / poly(2-ethylhexyl acrylate) copolymer in step S3.1 is 50-55°C.

10. The process for preparing a high-viscosity UV-resistant glue according to claim 4, characterized in that: Step S3.2: Slowly add the chlorinated polyvinyl chloride / poly(2-ethylhexyl acrylate) copolymer within 25-30 minutes.

Images