CN113603823B - Anti-ultraviolet repair material and preparation method and application thereof - Google Patents

Anti-ultraviolet repair material and preparation method and application thereof Download PDF

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CN113603823B
CN113603823B CN202111062284.3A CN202111062284A CN113603823B CN 113603823 B CN113603823 B CN 113603823B CN 202111062284 A CN202111062284 A CN 202111062284A CN 113603823 B CN113603823 B CN 113603823B
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repair material
ultraviolet
light shielding
ultraviolet light
shielding agent
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CN113603823A (en
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林木松
李智
郑晓光
唐念
付强
张晟
李健
黄正勇
钱艺华
张丽
赵耀洪
付程曦
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Guangdong Power Grid Co Ltd
Electric Power Research Institute of Guangdong Power Grid Co Ltd
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Guangdong Power Grid Co Ltd
Electric Power Research Institute of Guangdong Power Grid Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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Abstract

The invention discloses an anti-ultraviolet repair material and a preparation method and application thereof. The preparation method of the repair material comprises the following steps: modifying the inorganic ultraviolet light shielding agent by adopting cyclodextrin; and carrying out substitution reaction on the object molecules and thionyl chloride, reacting the product with hydroxyethyl methacrylate and triethylamine to obtain an object molecule with a double-bond structure, including the object molecule with an inorganic ultraviolet light shielding agent modified by beta-cyclodextrin, freeze-drying to obtain a host-object inclusion compound, mixing the host-object inclusion compound with an acrylic comonomer, an initiator, an accelerator and an active diluent, and carrying out polymerization reaction to obtain the ultraviolet-resistant repair material. The ultraviolet-resistant repair material disclosed by the invention has good ultraviolet light shielding capability and good light aging resistance, can repair damage for multiple times independently, does not need external condition stimulation, can restore the original performance, prolongs the service life of a cable sheath, and saves the cost of power grid construction and operation and maintenance.

Description

Anti-ultraviolet repair material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an ultraviolet-resistant repair material and a preparation method and application thereof.
Background
When the cable sheath insulating material is used, the cable sheath insulating material is aged and cracked under the action of oxygen and ultraviolet rays, so that the insulating property and the mechanical property of the cable sheath insulating material are reduced. At present, there are three main repair methods for insulation material damage: 1) filling a repairing liquid capable of performing polymerization reaction with water into the microscopic defects to generate colloidal organic polymers so as to repair the defects; 2) filling homogeneous insulating materials at the defects such as cracks and the like, and fusing new and old materials by utilizing hot welding for bonding and repairing; 3) and sleeving the defective area with the heat-shrinkable tube, and heating to shrink the sleeve to the tight package defect.
The three repair techniques have the following disadvantages: 1) the repairing liquid can only carry out polymerization reaction with water to generate a polymer for repairing defects; 2) hot weld repair can only repair thermoplastic defects; 3) the thickness of the insulating layer is increased by the heat-shrinkable tube, the heat dissipation difficulty is increased, and local overheating is easily caused; the heat shrinkable tube shrinks to the tight wrapping defect through heating, the sealing performance of the heat shrinkable tube and the base material is poor, and moisture is easy to permeate through the joint to cause insulation breakdown. Secondly, the three repairing modes need to depend on an accurate fault location technology, a fault point is influenced by a location distance and a fault object, and the accurate location difficulty is high. Moreover, the conventional repair materials do not have the performance of absorbing and shielding ultraviolet light, and the conventional repair technology also needs excavation and soil covering, wire disconnecting and power failure, which seriously affects the power production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an anti-ultraviolet repair material.
The invention also aims to provide a preparation method of the ultraviolet-resistant repair material.
The invention further aims to provide application of the ultraviolet-resistant repair material.
The purpose of the invention is realized by the following technical scheme: a preparation method of an ultraviolet-resistant repair material comprises the following steps:
(1) dispersing an inorganic ultraviolet light shielding agent in a beta-cyclodextrin (beta-CD) solution, carrying out ultraviolet irradiation and separation to obtain the cyclodextrin modified inorganic ultraviolet light shielding agent;
(2) carrying out substitution reaction on the object molecule and thionyl chloride to generate an acyl chloride organic intermediate product, and reacting the acyl chloride organic intermediate product with hydroxyethyl methacrylate (HEMA) and triethylamine to generate the object molecule with a double-bond structure;
(3) mixing the cyclodextrin modified inorganic ultraviolet light shielding agent in the step (1) with the guest molecules with double bond structures in the step (2), including, and freeze-drying to obtain a host-guest inclusion compound;
(4) and (4) dispersing the host-guest inclusion compound obtained in the step (3) in a solvent, adding an acrylic comonomer, an initiator, an accelerator and a reactive diluent, and carrying out polymerization reaction to obtain the ultraviolet-resistant repair material.
Preferably, the inorganic ultraviolet light-shielding agent in the step (1) is at least one of lead oxide, zinc barium, talcum powder and calcium carbonate.
Preferably, the particle size of the inorganic ultraviolet light shielding agent in the step (1) is 1-100 nm.
Preferably, the mass ratio of the beta-cyclodextrin to the inorganic ultraviolet light shielding agent in the step (1) is 1-10: 1; more preferably 5: 1.
preferably, the solvent in the beta-cyclodextrin solution of step (1) is water.
Preferably, the concentration of the beta-cyclodextrin solution in the step (1) is 10 g/L-15 g/L.
Preferably, the dispersing mode in the step (1) is ultrasonic dispersing for 20-40 min.
Preferably, the ultraviolet irradiation in the step (1) is performed for 40 to 60 hours under the power of 30 to 50W.
Preferably, the separation in step (1) is a centrifugal separation.
Preferably, the cyclodextrin modified inorganic ultraviolet light shielding agent in the step (1) is washed, lyophilized and then subjected to the next reaction.
Preferably, the guest molecule in the step (2) is at least one of adamantanecarboxylic acid, azobenzoic acid, ferrocenecarboxylic acid and ferroceneacetic acid.
Preferably, the molar weight ratio of the guest molecule, HEMA and triethylamine in the step (2) is 1-2: 1: 1-2; more preferably, the molar weight ratio is 1.5: 1: 1.3.
preferably, the thionyl chloride of step (2) is used in excess.
Preferably, the substitution reaction in the step (2) is a reaction at 50-100 ℃ for 1-2 h; more preferably, the reaction is at 80 ℃ for 2 h.
Preferably, after the substitution reaction in the step (2) is completed, excess thionyl chloride is removed by rotary evaporation.
Preferably, the acyl chloride organic intermediate product in the step (2) is dissolved by using a proper amount of solvent dichloromethane and then reacts with HEMA and triethylamine.
Preferably, the reaction time in the step (2) is 4-6 h; more preferably 5 h.
Preferably, the reaction of step (2) is a reaction under an ice bath.
Preferably, the guest molecule with a double bond structure in the step (2) is extracted and dried before the next reaction.
Preferably, the extraction is sequentially performed by using dilute hydrochloric acid, sodium bicarbonate solution and water.
Preferably, the concentration of the dilute hydrochloric acid is 1M.
Preferably, the concentration of the sodium bicarbonate solution is 1M.
Preferably, the drying is vacuum drying.
Preferably, the mass ratio of the cyclodextrin-modified inorganic ultraviolet light shielding agent in the step (3) to the guest molecule with a double bond structure is 2-30: 1; more preferably, the mass ratio is 22: 1.
preferably, the mixing in the step (3) adopts water as a solvent, and the amount is a proper amount.
Preferably, the inclusion mode in the step (3) is that ultrasonic dispersion is carried out for 20-40min and then stirring is carried out for 20-30 h; more preferably, the inclusion mode in the step (3) is that ultrasonic dispersion is carried out for 30min and then stirring is carried out for 24 h.
Preferably, the reactants of the polymerization reaction in the step (4) are mixed according to the following molar weight percentage: 5 to 12 percent of host-guest inclusion compound, 80 to 90 percent of acrylic comonomer, 0.3 to 3 percent of initiator, 0.1 to 1 percent of accelerant and 0.5 to 5 percent of active diluent.
Preferably, the solvent in the step (4) is ethanol, and the amount is a proper amount.
Preferably, the dispersion in the step (4) is ultrasonic dispersion for 40-60 min.
Preferably, the acrylic comonomer in step (4) is at least one of hydroxypropyl acrylate and hydroxybutyl acrylate.
Preferably, the initiator in the step (4) is at least one of dicumyl peroxide, tert-butyl hydroperoxide and benzoyl peroxide.
Preferably, the promoter in the step (4) is at least one of N, N-diethylaniline, sodium metabisulfite and mercaptan.
Preferably, the reactive diluent in the step (4) is at least one of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, hydroxyethyl acrylate and methyl methacrylate.
Preferably, the polymerization reaction of step (4) is carried out under an inert atmosphere; more preferably under argon or helium.
Preferably, the polymerization reaction in the step (4) is polymerization for 10-12 hours at 0-50 ℃; more preferably at 50 ℃ for 10 h.
An anti-ultraviolet repair material is prepared by the preparation method.
The application of the uvioresistant repair material in preparing the cable sheath.
Compared with the prior art, the invention has the following beneficial effects:
the invention solves the problem that the service life of the existing cable sheath material is short due to the influence of external factors such as ultraviolet light, oxygen and the like. Meanwhile, the defects of the conventional repair technology do not exist: depending on an accurate fault location technology, earth covering needs to be excavated, stitches are removed, and power is cut off, so that power production is seriously affected. The ultraviolet-resistant repair material disclosed by the invention has good ultraviolet light shielding capability and good light aging resistance, can be used for autonomously repairing damage for multiple times, does not need external condition stimulation, can restore the original performance, prolongs the service life of a cable sheath, and saves the cost of power grid construction and operation and maintenance.
Drawings
FIG. 1 is a graph showing the result of testing the self-repairing ability of an ultraviolet resistant repairing material; wherein, A is the initial cross-sectional area of the notch, and B is the cross-sectional area of the notch after self-repairing.
FIG. 2 is a graph showing the result of the self-repairing capability of the coating of the ultraviolet resistant repairing material; wherein, UV-1 is an experimental group of coating the outer surface of the test tube with an anti-ultraviolet repair material, and UV-2 is a control group of coating the outer surface of the test tube with Nippon paint.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of host molecule: dissolving 1g of beta-cyclodextrin (beta-CD) in 100mL of water, and then dispersing 0.2g of nano PbO with the granularity (less than or equal to 20nm) into the beta-CD solution by an ultrasonic method, wherein the ultrasonic time is controlled to be 40 min; irradiating the dispersion liquid for 50h under a 50W ultraviolet lamp, separating by adopting a high-speed refrigerated centrifuge to obtain a solid product, washing the solid product for 5 times by using purified water, and freeze-drying to obtain the main molecular cyclodextrin modified inorganic ultraviolet light shielding agent beta-CD-PbO.
Preparation of guest molecules: dissolving 12.8mmol Ad-COOH (adamantane carboxylic acid) in 20mL thionyl chloride, reacting for 2h at the temperature of 80 ℃, and removing excessive thionyl chloride by using a rotary evaporator to generate 12.8mmol of acyl chloride organic intermediate Ad-COCl (adamantane carbonyl chloride); dissolving Ad-COCl in 100mL of anhydrous dichloromethane, dripping into 8.3mmol of HEMA and 11.5mmol of triethylamine, reacting for 5 hours under the ice bath condition, sequentially extracting with 1M of dilute hydrochloric acid, 1M of sodium bicarbonate solution and purified water, and drying the extract in a vacuum drying oven to generate the guest molecule HEMA-Ad with the double bond structure.
And (3) generation of a host-guest inclusion compound: mixing 10mg of HEMA-Ad and 220mg of beta-CD-PbO into 6.0mL of purified water, carrying out ultrasonic treatment for 30min, stirring for 24h to complete host-guest group inclusion, and freeze-drying the inclusion solution to obtain the host-guest inclusion compound HEMA-Ad/beta-CD-PbO.
Polymerization reaction: dispersing the prepared HEMA-Ad/beta-CD-PbO1.05mmol into 6.0mL ethanol by an ultrasonic method, carrying out ultrasonic treatment for 50min, sequentially adding 8.4mmol of hydroxypropyl acrylate, adding 0.030mmol of initiator tert-butyl hydroperoxide, 0.015mmol of promoter sodium metabisulfite and 0.076mmol of active diluent trimethylolpropane triacrylate, uniformly mixing, and polymerizing for 10h at 50 ℃ in an argon or helium environment to finally prepare the ultraviolet-resistant repair material.
And (3) detecting the tensile property of the ultraviolet-resistant repair material: in order to detect the tensile property of the ultraviolet-resistant repair material, the ultraviolet-resistant repair material is detected by a universal tensile tester (AG-10 TA); and directly copolymerizing hydroxypropyl acrylate, an initiator, an accelerator and a reactive diluent to prepare a contrast material without adding a host-guest inclusion compound HEMA-Ad/beta-CD-PbO. The detection result shows that the tensile strength of the comparative material can reach 2.03MPa, and the tensile strength of the ultraviolet-resistant repair material can reach 4.50MPa, which indicates that the introduction of HEMA-Ad/beta-CD-PbO significantly enhances the mechanical property of the material.
And (3) detecting the wear resistance of the ultraviolet-resistant repair material (GB 1689 vulcanized rubber wear resistance measurement): the abrasion resistance test weight loss of the ultraviolet-resistant repair material prepared in the embodiment 1 is 0.07g, the weight loss of the Nippon paint is 0.12g, and the abrasion resistance of the ultraviolet-resistant repair material is obviously superior to that of the Nippon paint.
The hydrophobic property of the ultraviolet resistant repair material is as follows: the contact angle of the ultraviolet-resistant repair material is 100 degrees, and the ultraviolet-resistant repair material has good hydrophobicity.
In order to verify the anti-photoaging capability of the anti-ultraviolet repair material, an insulating material PVC is used as a base material, the anti-ultraviolet repair material is coated, a PVC sample which is not coated with the anti-ultraviolet repair material is used as a comparison sample, the two comparison samples are put into a BL-GHX-V photochemical reaction instrument to accelerate photoaging for 24 hours, and the result is as follows: after accelerated photoaging, the sample without the ultraviolet-resistant repair material is yellow, and the sample without the ultraviolet-resistant repair material is not discolored, which is basically the same as the original PVC sample, thus indicating that the ultraviolet-resistant repair material prepared in example 1 has good photoaging resistance.
In order to verify the self-repairing capability of the ultraviolet-resistant repairing material, a repairing layer formed after the repairing material is dried and solidified is cut off by a knife, then two sections are contacted together, after the repairing layer is placed for 12 hours, the sections are observed by a 3D super-depth-of-field microscope, the result is shown in figure 2, and the initial cross-sectional area of a cut is 7282 mu m2 Cross-sectional area 0 μm after self-repair of the notch2Indicating that the incision has been completely repaired. The self-repairing efficiency is 100%, and the formula is as follows:
Figure BDA0003256830830000061
in the formula: eta is self-repairing efficiency, S0The initial cross-sectional area of the notch is S, and the cross-sectional area of the notch after self-repairing is S.
In order to verify the shielding capability of the ultraviolet light after the ultraviolet-resistant repair material coating is self-repaired, rhodamine B which can be degraded under the irradiation of ultraviolet light is adopted for testing. Two groups of quartz test tubes are respectively filled with 6mL of rhodamine B solution with the concentration of 0.12mg/L, wherein the outer surface of the first group of test tubes is coated with an anti-ultraviolet repair material, the outer surface of the second group of test tubes is coated with Nippon paint, then scratches are respectively scratched on the paint by a knife, the outer surface of each quartz test tube is covered by wet filter paper, the quartz test tubes are placed for 24 hours, and then ultraviolet irradiation is carried out for 24 hours. The results are shown in FIG. 2, where the concentration of rhodamine B in group 1 is 0.12mg/L and the concentration of rhodamine B in group 2 is 0.09mg/L, so the degree of degradation in group 1 is 0 and the degree of degradation in group 2 is 25%, calculated as follows:
Figure BDA0003256830830000071
therefore, the ultraviolet light is shielded by the test tube coated with the ultraviolet-resistant repair material due to self-repairing of the coating, so that rhodamine B is not degraded, the coating coated with the Nippon coating cannot be self-repaired, and the ultraviolet light irradiates the rhodamine B solution through scratches to be degraded. The self-repairing of the coating of the anti-ultraviolet electric repairing material not only restores the appearance of the material, but also restores the shielding effect on ultraviolet light.
Comparative example 1
Verification of Nano PbO and Nano Al2O3The difference between ultraviolet absorption and shielding capability is that the nano Al is added according to the following steps2O3The self-repairing high molecular polymer:
(1) preparation of host molecules
50g of beta-CD cyclodextrin was dispersed in 1200mL of deionized water. 13g of p-toluenesulfonyl chloride are then added slowly with vigorous stirring. The reaction was allowed to proceed overnight, 20g NaOH was added, excess p-toluenesulfonyl chloride was removed by filtration, and ammonium chloride was added until the pH of the solution was 8. The solution was then placed in a refrigerator at 4 ℃ overnight and the precipitated product was obtained by suction filtration. And (3) re-dissolving the white precipitate in deionized water to perform recrystallization, and repeating the recrystallization process for 2 times to obtain TOS-CD. 0.5g of aminated alumina microspheres (NH)2-Al2O3NPs) are dissolved in 25mL of dimethyl sulfoxide (DMSO), stirred vigorously for 30min, 8g of TOS-CD are added, when TOS-CD is completely dissolved, the pH is adjusted to 8(1mol/L of dilute hydrochloric acid), and then the mixture is heated to 65 ℃ under the protection of inert gas and reactedRemoving dimethyl sulfoxide by centrifugation for 12h, washing with ethanol for 3 times, and evaporating solvent to obtain CD-Al2O3 NPs。
(2) Preparation of guest molecules
2.3g of adamantanecarboxylic acid (Ad-COOH) was dissolved in 50mL of thionyl chloride, and stirred at 90 ℃ for 5 hours, and excess thionyl chloride was spin-dried to obtain adamantanoyl chloride. 1mL of 2-hydroxyethyl-methacrylate (HEMA) and 1.6mL of triethylamine were dissolved in 100mL of dichloromethane at 0 ℃ to give a mixture which was reacted with adamantanoyl chloride. Dissolving the adamantane chloride obtained in the last step in 30mL of dichloromethane, slowly dripping the mixture into the mixture, reacting overnight, washing a light yellow reaction solution by using a 1mol/L hydrochloric acid solution, 1mol/L sodium bicarbonate and deionized water (washing for three times), adding anhydrous sodium sulfate, filtering out solids, and finally evaporating the redundant solvent to obtain the HEMA-Ad.
(3) Copolymerization reaction
0.3g CD-Al2O3NPs are dispersed in 3mL of N, N-Dimethylformamide (DMF) and subjected to ultrasonic treatment for 30min, and then 0.6g of HEMA-Ad is added and stirred for 24h to realize the interaction between a host and a guest; then 0.66g polyvinylpyrrolidone (PVP), 0.5mL 2-hydroxyethyl-methacrylate (HEMA), 2.37mL Butyl Acrylate (BA) and 0.1 microliter cross-linker Ethylene Glycol Dimethacrylate (EGDMA) were added in sequence in proportion, and after stirring 10mg initiator Azobisisobutyronitrile (AIBN) was added. Stirring and reacting at 75 ℃, stopping stirring when the viscosity of the system is increased, sucking a rotor by a magnet, continuing to react for 10 hours at 75 ℃, and finally placing the obtained material in a vacuum oven to remove the solvent to obtain the high molecular compound with the self-repairing function.
The repair material prepared in example 1 and the comparative sample obtained in comparative example were tested for their respective uv-equivalent attenuation rates, with the uv-equivalent attenuation rate of the comparative sample being 39.1% and the repair material prepared in example 1 being 98.4%, indicating that the repair material prepared in example 1 has much greater ability to shield uv rays than the comparative sample.
Comparative example 2
The initiator tert-butyl hydroperoxide and the promoter sodium metabisulfite in the example 1 are replaced by the initiator azobisisobutyronitrile (the addition amount is 0.030mmol), the reaction temperature is changed to 55 ℃, the reaction time is 15h, and other steps are not changed. The results show that using azobisisobutyronitrile as initiator, the reaction temperature was 55 deg.C, the reaction time was 15 hours and the reaction temperature was 50 deg.C for example 1 and the reaction time was 10 hours. The result shows that the redox initiator can initiate polymerization reaction at lower temperature (0-50 ℃) compared with the thermal decomposition initiator, and the reaction rate is improved.
Comparative example 3
The reactive diluent of example 1 was removed and the other steps were unchanged. The viscosity and adhesion detection of the obtained sample shows that the viscosity of the repair material obtained by adding the reactive diluent is reduced by 20% compared with that of the sample, and the coating construction is facilitated; the adhesion was improved to a level of 4, while the adhesion of this sample was a level of 2.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (8)

1. The preparation method of the ultraviolet-resistant repair material is characterized by comprising the following steps of:
(1) dispersing an inorganic ultraviolet light shielding agent in a beta-cyclodextrin solution, carrying out ultraviolet irradiation and separation to obtain a cyclodextrin modified inorganic ultraviolet light shielding agent;
(2) carrying out substitution reaction on the object molecule and thionyl chloride to generate an acyl chloride organic intermediate product, and reacting the acyl chloride organic intermediate product with hydroxyethyl methacrylate and triethylamine to generate the object molecule with a double-bond structure;
(3) mixing the cyclodextrin modified inorganic ultraviolet light shielding agent in the step (1) with the guest molecules with double bond structures in the step (2), including, and freeze-drying to obtain a host-guest inclusion compound;
(4) dispersing the host-guest inclusion compound in the step (3) in a solvent, adding an acrylic comonomer, an initiator, an accelerator and an active diluent, and carrying out polymerization reaction to obtain an ultraviolet-resistant repair material;
the guest molecule in the step (2) is adamantanecarboxylic acid;
the inorganic ultraviolet light shielding agent in the step (1) is nano PbO; the particle size of the inorganic ultraviolet light shielding agent in the step (1) is 1-100 nm;
the acrylic acid comonomer in the step (4) is at least one of hydroxypropyl acrylate and hydroxybutyl acrylate;
the initiator in the step (4) is at least one of dicumyl peroxide, tert-butyl hydroperoxide and benzoyl peroxide;
the accelerant in the step (4) is at least one of N, N-diethylaniline, sodium metabisulfite and mercaptan;
the reactive diluent in the step (4) is at least one of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, hydroxyethyl acrylate and methyl methacrylate;
the mass ratio of the beta-cyclodextrin to the inorganic ultraviolet light shielding agent in the step (1) is 1-10: 1;
the molar weight ratio of the guest molecule, hydroxyethyl methacrylate and triethylamine in the step (2) is 1-2: 1: 1-2;
the mass ratio of the cyclodextrin modified inorganic ultraviolet light shielding agent to the guest molecule with the double bond structure in the step (3) is 2-30: 1;
the reactants of the polymerization reaction in the step (4) are prepared according to the following molar weight percentage: 5-10% of a host-guest inclusion compound, 80-90% of an acrylic comonomer, 2-3% of an initiator, 0.5-1% of an accelerant and 2-5% of an active diluent.
2. The method for preparing the ultraviolet resistant repair material according to claim 1,
the mass ratio of the beta-cyclodextrin to the inorganic ultraviolet light shielding agent in the step (1) is 5: 1;
the molar weight ratio of the guest molecules, hydroxyethyl methacrylate and triethylamine in the step (2) is 1.5: 1: 1.3;
the mass ratio of the cyclodextrin modified inorganic ultraviolet light shielding agent to the guest molecule with the double bond structure in the step (3) is 22: 1.
3. the method for preparing the ultraviolet resistance repair material according to claim 1,
the concentration of the beta-cyclodextrin solution in the step (1) is 10 g/L-15 g/L;
the separation in the step (1) is centrifugal separation;
the dispersing mode in the step (1) is ultrasonic dispersing for 40-60 min;
washing the cyclodextrin modified inorganic ultraviolet light shielding agent in the step (1), freeze-drying, and carrying out the next reaction;
removing excessive thionyl chloride by adopting a rotary evaporation mode after the substitution reaction in the step (2) is finished;
reacting the acyl chloride organic intermediate product in the step (2) with hydroxyethyl methacrylate and triethylamine in ice bath;
extracting and drying the guest molecules with the double bond structures in the step (2) and then carrying out the next reaction;
the dispersion in the step (4) is ultrasonic dispersion for 40-60 min;
and (4) carrying out the polymerization reaction under an inert atmosphere.
4. The method for preparing the ultraviolet resistant repair material according to claim 3,
the extraction is to adopt dilute hydrochloric acid, sodium bicarbonate solution and water for extraction in sequence;
the concentration of the dilute hydrochloric acid is 1M;
the concentration of the sodium bicarbonate solution is 1M;
the drying is vacuum drying;
and (5) carrying out the polymerization reaction in the step (4) under argon or helium.
5. The method for preparing the ultraviolet resistant repair material according to claim 1,
irradiating for 40-60 h under the power of 30-50W in the ultraviolet irradiation in the step (1);
the substitution reaction in the step (2) is a reaction at 50-100 ℃ for 1-2 h;
the reaction time of the acyl chloride organic intermediate product in the step (2) with hydroxyethyl methacrylate and triethylamine is 4-6 h;
the inclusion mode in the step (3) is that ultrasonic dispersion is carried out for 20-40min and then stirring is carried out for 20-30 h;
the polymerization reaction in the step (4) is polymerization for 10-12 h at 0-50 ℃;
the solvent in the beta-cyclodextrin solution in the step (1) is water;
the dosage of the thionyl chloride in the step (2) is excessive;
dissolving the acyl chloride organic intermediate product in a proper amount of solvent dichloromethane, and reacting with hydroxyethyl methacrylate and triethylamine in the step (2);
in the step (3), water is used as a solvent, and the amount of the water is proper;
the solvent in the step (4) is ethanol, and the dosage is proper.
6. The method for preparing the ultraviolet resistant repair material according to claim 5,
the substitution reaction in the step (2) is carried out for 2 hours at the temperature of 80 ℃;
the reaction time of the acyl chloride organic intermediate product in the step (2) with hydroxyethyl methacrylate and triethylamine is 5 h;
the inclusion mode in the step (3) is that ultrasonic dispersion is carried out for 30min and then stirring is carried out for 24 h;
the polymerization reaction in the step (4) is polymerization for 10 hours at 50 ℃.
7. An ultraviolet-resistant repair material, which is prepared by the preparation method of any one of claims 1 to 6.
8. Use of the uv-resistant repair material according to claim 7 for the preparation of a cable sheath.
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