CN114316759B - Fiber-reinforced UV curing repair material and preparation method thereof - Google Patents
Fiber-reinforced UV curing repair material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fiber-reinforced UV curing repair material and a preparation method thereof, wherein the repair material is prepared from unsaturated polyester resin, reinforced fibers, a polymerization inhibitor, a photosensitizer and a diluent in a mass ratio of 1: 0.04-0.07: 0.004 to 0.005: 0.04-0.05: 0.5 to 0.6; wherein, the reinforced fiber is obtained by ultrasonically compounding modified carbon fiber subjected to surface activation and oxidation treatment and aramid fiber subjected to low-temperature plasma surface modification under the dispersion action of a silane coupling agent; the unsaturated polyester resin is prepared by firstly carrying out catalytic polycondensation on dihydric alcohol and saturated dibasic acid, then carrying out polycondensation on the dihydric alcohol and the unsaturated dibasic acid again, carrying out end sealing on the polycondensate to obtain unsaturated polyester resin, and finally adding reinforcing fibers, a photosensitizer, a polymerization inhibitor and a diluent into the unsaturated polyester resin to obtain the fiber-reinforced UV curing repair material.
Description
Technical Field
The invention relates to a fiber-reinforced UV curing repair material and a preparation method thereof.
Background
The UV curing trenchless pipeline repairing technology is rapidly developed and applied due to the advantages of high repairing speed, high repairing quality, stability, reliability, short plugging time of construction and the like. With the development of social economy, the fields of tunnels, oil and gas, ocean engineering and the like put forward higher requirements on UV curing trenchless pipeline repairing materials, the existing pipeline repairing materials are increasingly difficult to meet the industrial requirements, and new pipeline repairing materials are urgently needed to be developed.
The existing UV-cured trenchless pipeline repairing material mainly comprises resin and a reinforcing material. Although the unsaturated polyester resin which is mainly used at present is low in price and easy to prepare in a large amount, the chemical properties of acid and alkali resistance, water resistance, solvent resistance and the like are general after ultraviolet curing, so that the problems of high volume shrinkage rate and large deformation exist, the mechanical properties of impact resistance, bending resistance, adhesive force and the like are poor, and the performance requirements on the pipeline repairing material under complex environments cannot be met; styrene is widely used as a crosslinking diluent in the resin formula, has pungent smell and carcinogenicity, and is not friendly to the environment and human bodies; meanwhile, oxygen in the air has an inhibiting effect on the crosslinking curing reaction during ultraviolet curing, so that the cured resin has the problems of slow drying, sticky surface and the like. The traditional glass fiber reinforced material has the defects of redundant rigidity, insufficient wear resistance and flexibility and is not suitable for being used as a reinforced material of a long-distance conveying pipeline repairing material. The carbon fiber has the characteristics of high strength and high modulus, the aramid fiber has excellent chemical corrosion resistance, good wear resistance, light weight and the like, so that the carbon fiber and the aramid fiber have the capability of being qualified as a reinforcing material in a pipeline repairing material. Although the carbon fiber and the aramid fiber can replace the traditional glass fiber to be used as a reinforcing material, the fibers and the resin are difficult to fuse at intervals, and the bonding property is poor, so the surface treatment is required to be carried out on the fibers, and the fibers can be put into use after the interface compatibility is improved.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a UV curing repair material with good bonding force between reinforced fibers and matrix resin, which is characterized in that the fibers are subjected to surface modification to ensure that the fibers and the matrix resin have good bonding force; the invention also aims to provide a preparation method of the repair material, which effectively improves the chemical property and the mechanical property of the UV curing repair material by developing a new formula and a preparation process of unsaturated polyester resin.
The technical scheme is as follows: the fiber-reinforced UV curing repair material comprises the following components in percentage by mass: 0.04-0.07: 0.004 to 0.005: 0.04-0.05: 0.5-0.6 of unsaturated polyester resin, reinforcing fiber, polymerization inhibitor, photosensitizer and diluent.
Wherein the viscosity of the repairing material is 0.75-1.5Pa.s; the acid value is 20-35 mgKOH/g.
Wherein the unsaturated polyester resin is prepared by the following method: and in an inert gas atmosphere, carrying out polycondensation reaction on dihydric alcohol and saturated dibasic acid under the action of an organotin catalyst at high temperature, adding unsaturated dibasic acid into the mixture after the reaction, carrying out polycondensation reaction again, adding a terminating agent after the reaction, and carrying out terminating reaction to obtain the unsaturated polyester resin. The unsaturated polyester resin is synthesized by adopting a melt polycondensation mode, the reactant concentration is higher, less impurities are introduced, and the production efficiency is higher. Saturated dibasic acid is added into a reaction system of the dibasic alcohol and the unsaturated dibasic acid, and the dibasic alcohol and the saturated dibasic acid are subjected to polycondensation reaction firstly and then are subjected to polycondensation reaction with the unsaturated dibasic acid, so that the tendency of crystallization of a polymerization product of the dibasic alcohol and the unsaturated dibasic acid can be effectively inhibited.
Wherein the dihydric alcohol is neopentyl glycol and 1, 2-propylene glycol according to a mass ratio of 1-3.5: 1; the saturated binary acid is isophthalic acid and phthalic acid according to the mass ratio of 0.5-3.5: 1; the unsaturated dibasic acid is fumaric anhydride; the end-capping agent is pentaerythritol triallyl ether; the organic tin catalyst is monobutyl tin oxide or dibutyltin dilaurate. The dihydric alcohol is a composition of neopentyl glycol and 1, 2-propylene glycol, the specific neopentyl glycol of the neopentyl glycol can improve the strength, water resistance and corrosion resistance of the resin, and the chain structure of the 1, 2-propylene glycol can maintain the moderate viscosity of the resin, so that the fluidity and the processability of the resin are ensured; the saturated dibasic acid is a composition of phthalic acid and isophthalic acid, the mechanical property and the chemical property of the resin can be considered, the unsaturated dibasic acid is fumaric anhydride, and the trans structure has milder activity than the cis structure, so that the risk of implosion in the synthesis process can be reduced. In the synthetic process of the unsaturated polyester resin, an end capping agent pentaerythritol triallyl ether is introduced for end capping, allyl with higher activity is preferentially combined with oxygen in the air, unsaturated double bonds in the resin are protected from being oxidized by the oxygen in the air in the curing process, so that the polymerization inhibition effect of the oxygen in the air on opening mutual crosslinking of the unsaturated double bonds is weakened, and the problems of stickiness and slow drying of the surface layer of the material after the resin is cured are solved.
Wherein the mass ratio of the dihydric alcohol to the saturated dibasic acid to the unsaturated dibasic acid to the blocking agent to the organotin catalyst is 1:1 to 1.05:0.6 to 0.75:0.3 to 0.45: 0.013-0.014.
The reinforcing fiber is obtained by compounding modified carbon fibers and modified aramid fibers in a mass ratio of 1 (0.6-0.7) under the action of a silane coupling agent.
The modified carbon fiber is prepared by the following method: after being cleaned and dried, the carbon fiber is firstly soaked and activated by rare earth salt water solution and then is prepared by oxidizing treatment by an oxidant after activation. The carbon fiber is soaked in the rare earth salt solution, the rare earth can change the surface charge distribution of the carbon fiber, the activity is improved, the oxidation effect during the subsequent oxidation by hydrogen peroxide is facilitated, the whole process is carried out at normal temperature and normal pressure, the problem that the highly corrosive substances are inconvenient to process and the carbon fiber structure is damaged can be solved by adopting the mild oxidation mode, the oxidation effect same as that of the highly corrosive substances can be achieved, and the fusion of the fiber and the resin is effectively improved.
Wherein the rare earth salt is lanthanum chloride or cerium nitrate; the mild oxidant is 10-20 wt.% aqueous hydrogen peroxide or 5-10 wt.% aqueous sodium hypochlorite.
The modified aramid fiber is prepared by the following method: placing aramid fiber in a vacuum reactor at room temperature, heating to 200-300 ℃, vacuumizing, then filling mixed reaction gas, discharging the mixed gas by a radio-frequency electrode, performing low-temperature plasma surface treatment on the aramid fiber, vacuumizing after the surface treatment is completed, and then filling inert gas to normal pressure to obtain the modified aramid fiber. The invention uses low-temperature plasma for modification, improves the polarity of the surface of the aramid fiber through the plasma, forms reactive sites on the surface of the fiber, improves the wettability of the fiber, improves the mechanical property and simultaneously improves the fusion property of the fiber and resin.
Wherein the silane coupling agent is gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane coupling agent; the mass ratio of the addition amount to the modified carbon fiber is 1.4-1.5.
The preparation method of the fiber-reinforced UV curing repair material specifically comprises the following steps: and (2) cooling the synthesized unsaturated polyester resin to 100-120 ℃ in an inert gas atmosphere, adding the polymerization inhibitor, the reinforcing fiber, the photosensitizer and the diluent into the unsaturated polyester resin in the formula ratio in sequence, and stirring to obtain the pipeline repairing material. When the temperature is higher than the temperature range, part of the added substances are destroyed and decomposed, and when the temperature is lower than the temperature range, the viscosity of the unsaturated polyester resin is increased, the subsequent processing is difficult, and other substances are difficult to fuse with the resin after being added, so that the substances cannot be uniformly dispersed in a resin system.
Wherein the polymerization inhibitor is hydroquinone or p-hydroxyanisole; the photosensitizer is benzoin dimethyl ether or benzoin ethyl ether; the diluent is ethoxylated trimethylolpropane triacrylate.
Has the advantages that: compared with the prior art, the invention has the remarkable advantages that: on one hand, the repair material of the invention, on the one hand, through the adjustment of the preparation raw materials and the preparation process of the unsaturated polyester resin, ensures that the obtained unsaturated polyester resin matrix has good strength, water resistance and corrosion resistance, and simultaneously can weaken the polymerization inhibition effect of oxygen in the air, and solves the problems of slow surface drying and sticky surface existing in the cured resin, so that the surface drying time and the actual drying time of the repair material are both greatly reduced after the repair material is cured under the irradiation of ultraviolet light; on the other hand, the modified carbon fiber surface contains a large number of active functional groups such as carboxyl, hydroxyl, epoxy and the like through modifying the reinforcing fiber, the reactivity of the fiber surface is greatly improved compared with that before modification, the surface roughness of the aramid fiber is improved, the surface energy is increased, the wettability and the adhesive force of the fiber are improved, meanwhile, the reinforcing fiber prepared under the coupling action of the coupling agent can effectively enhance the bonding force between the fiber and a resin matrix, the dispersibility of the fiber among resins is improved, so that the repairing material has the advantages of high strength, corrosion resistance and tear resistance and wear resistance of the aramid fiber, and the mechanical property and the chemical property of the repairing material are obviously improved; finally, the repairing material does not contain a styrene diluent, meets the requirements of environmental protection, has small harm to the environment and people in the construction process, selects the ethoxylated trimethylolpropane triacrylate as the diluent, ensures that the repairing material has higher cross-linking curing reaction activity under the irradiation of ultraviolet light due to the allyl active double bond contained in the ethoxylated trimethylolpropane triacrylate, has low volume shrinkage rate and small deformation of the cured repairing material due to the characteristics of macromolecular groups and high functionality, and has high mechanical strength and hardness, and the long-chain structure of ethoxy and ether bonds in the molecular structure ensures the flexibility of the resin after curing, so that the repairing material has good adhesive force with a coated substrate.
Drawings
FIG. 1 is an infrared spectrum of an unsaturated polyester resin obtained in example 2;
FIG. 2 is a scanning electron microscope image of the fiber-reinforced UV-curable repair material prepared in example 2 after curing.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The preparation method of the fiber-reinforced UV curing repair material comprises the following steps:
(1) Washing 3g of carbon fiber with 5mL of absolute ethyl alcohol for 2 times at 25 ℃, then washing with 5mL of deionized water for 3 times, drying for 2 hours at 90 ℃, cooling to room temperature, immersing with 15g of 0.5wt.% lanthanum chloride aqueous solution for 3 hours to obtain activated carbon fiber, immersing the activated carbon fiber in 15g of 10wt.% hydrogen peroxide aqueous solution, immersing for 5 hours, filtering, and drying at 120 ℃ for 3 hours to obtain modified carbon fiber;
(2) At the temperature of 25 ℃, 2g of aramid fiber is placed in a vacuum reactor, the temperature is raised to 200 ℃, the vacuum is pumped until the pressure is less than-0.07 Mpa, and the filling molar ratio is 12:1, the pressure of the mixed gas of carbon tetrachloride and ammonia gas is 0.05Mpa, and the radio-frequency electrode is under 60KV voltage, 4W/m 3 Discharging power to the reactor for 1.5h, vacuumizing to pressure less than-0.08 MPa, and charging N 2 Cooling to normal pressure to obtain modified aramid fiber;
(3) Uniformly mixing 3g of modified carbon fiber and 2g of modified aramid fiber at 25 ℃, ultrasonically oscillating at 300W, uniformly dispersing 2.13g of gamma-methacryloxypropyltrimethoxysilane coupling agent on the mixed fiber by using an atomizer, and spraying for 10min to obtain a reinforced fiber;
(4) 6g of 1, 2-propylene glycol, 12g of neopentyl glycol, 9.9g of phthalic acid, 9g of isophthalic acid and 0.25g of monobutyl tin oxide are added into a reaction kettle at the temperature of 25 ℃ and are stirred uniformly, and N 2 Heating to 200 ℃ under the atmosphere, reacting for 45min, cooling to 120 ℃, adding 12g of fumaric anhydride, heating to 200 ℃ again, reacting for 45min, adding 7g of pentaerythritol triallyl ether, and carrying out end-capping reaction for 30min to obtain unsaturated polyester resin;
(5)N 2 under the atmosphere, unsaturated polyester resin is addedAnd cooling the resin to 110 ℃, sequentially adding 0.25g of hydroquinone, 2.5g of reinforcing fiber, 2.5g of benzoin dimethyl ether and 30g of ethoxylated trimethylolpropane triacrylate, stirring for 15min, and cooling to obtain the fiber-reinforced UV curing repair material.
The prepared repairing material is brushed on a tinplate with the size of 120mm x 50mm x 0.28mm, and the tinplate is irradiated for 3min by ultraviolet light with the wavelength of 360nm emitted by an ultraviolet lamp with the power of 800W, so that cross-linking curing is carried out. And after the solidification is finished, placing the tinplate at a drying and ventilating place, drying for more than 24 hours, and testing.
Tests prove that the volume shrinkage of the fiber-reinforced UV curing repair material after curing is 7%, the surface drying time and the actual drying time are respectively 20s and 60s, the impact strength is 18000g.cm, the flexibility is 5mm, and the adhesive force is grade 2.
Example 2
The preparation method of the fiber-reinforced UV curing repair material specifically comprises the following steps:
(1) Washing 3g of carbon fiber with 5mL of absolute ethyl alcohol for 2 times at 25 ℃, then washing with 5mL of deionized water for 3 times, drying for 2 hours at 90 ℃, cooling to room temperature, immersing with 15g of 0.5wt.% lanthanum chloride aqueous solution for 3 hours to obtain activated carbon fiber, immersing the activated carbon fiber in 15g of 10wt.% hydrogen peroxide aqueous solution, immersing for 5 hours, filtering, and drying at 120 ℃ for 3 hours to obtain modified carbon fiber;
(2) At the temperature of 25 ℃, 2g of aramid fiber is placed in a vacuum reactor, the temperature is raised to 200 ℃, the vacuum is pumped until the pressure is less than-0.07 Mpa, and the filling molar ratio is 12:1, the pressure of the mixed gas of carbon tetrachloride and ammonia gas is 0.05Mpa, and the radio-frequency electrode is under 60KV voltage, 4W/m 3 Discharging the reactor for 1.5h, vacuumizing to a pressure of less than-0.08 MPa, and charging N 2 Cooling to normal pressure to obtain modified aramid fiber;
(3) Uniformly mixing 3g of modified carbon fiber and 1.8g of modified aramid fiber at 25 ℃, ultrasonically oscillating at 300W, uniformly dispersing 2g of gamma-methacryloxypropyltrimethoxysilane coupling agent on the mixed fiber by using an atomizer, and spraying for 10min to obtain a reinforced fiber;
(4)25℃next, 4g of 1, 2-propanediol, 14g of neopentyl glycol, 6g of phthalic acid, 12g of isophthalic acid and 0.25g of monobutyl tin oxide were added to the reaction kettle and stirred uniformly, and N 2 Heating to 200 ℃ under the atmosphere, reacting for 45min, cooling to 120 ℃, adding 13g of fumaric anhydride, heating to 200 ℃ again, reacting for 45min, adding 6g of pentaerythritol triallyl ether, and carrying out end-capping reaction for 30min to obtain unsaturated polyester resin;
(5)N 2 and (2) cooling the unsaturated polyester resin to 110 ℃ in the atmosphere, sequentially adding 0.25g of hydroquinone, 2.5g of reinforcing fiber, 2.5g of benzoin dimethyl ether and 32g of ethoxylated trimethylolpropane triacrylate, stirring for 15min, and cooling to obtain the fiber-reinforced UV curing repair material.
The prepared repairing material is brushed on a tinplate with the size of 120mm x 50mm x 0.28mm, and the tinplate is irradiated for 3min by ultraviolet light with the wavelength of 360nm emitted by an ultraviolet lamp with the power of 800W, so that cross-linking curing is carried out. And after the solidification is finished, placing the tinplate at a drying and ventilating place, drying for more than 24 hours, and testing.
Tests prove that the volume shrinkage of the fiber-reinforced UV curing repair material after curing is 5%, the surface and actual drying time is 15s and 45s respectively, the impact strength is 21000g.cm, the flexibility is 5mm, and the adhesive force is 0 grade.
In the infrared spectrum of FIG. 1, 1720cm -1 And 1250cm -1 The peaks of stretching vibration of C = O double bond and C-O-R bond in ester bond appeared nearby, respectively, 3000cm -1 The peak of moderate intensity is C-H bond stretching vibration peak of carbon atom on C = C bond, 1000cm -1 The nearby moderate intensity peak is the peak of bending vibration out of the C-H bond plane for the carbon atoms on the C = C bond; the above characteristic peaks indicate that the substance to be measured has two characteristic functional groups, i.e., an ester bond and an unsaturated carbon-carbon double bond, and it can be confirmed that the substance to be measured is an unsaturated polyester resin.
In the scanning electron microscope image of fig. 2, the granular material is carbon fiber, the strip-shaped material is aramid fiber, and the background is unsaturated polyester resin which is cross-linked with the diluent after being cured by UV, so that no obvious phase interface exists between the fiber and the resin, and the fusion degree is good.
Example 3
The preparation method of the fiber-reinforced UV curing repair material comprises the following steps:
(1) Washing 3g of carbon fiber with 5mL of absolute ethyl alcohol for 2 times at 25 ℃, then washing with 5mL of deionized water for 3 times, drying for 2 hours at 90 ℃, cooling to room temperature, immersing with 15g of 0.5wt.% lanthanum chloride aqueous solution for 3 hours to obtain activated carbon fiber, immersing the activated carbon fiber in 15g of 10wt.% hydrogen peroxide aqueous solution, immersing for 5 hours, filtering, and drying at 120 ℃ for 3 hours to obtain modified carbon fiber;
(2) At the temperature of 25 ℃, 2g of aramid fiber is placed in a vacuum reactor, the temperature is raised to 200 ℃, the vacuum is pumped until the pressure is less than-0.07 Mpa, and the filling molar ratio is 12:1, the pressure of the mixed gas of carbon tetrachloride and ammonia is 0.05Mpa, the radio-frequency electrode is at 60KV voltage, 4W/m 3 Discharging power to the reactor for 1.5h, vacuumizing to pressure less than-0.08 MPa, and charging N 2 Cooling to normal pressure to obtain modified aramid fibers;
(3) Uniformly mixing 3g of modified carbon fiber and 2.1g of modified aramid fiber at 25 ℃, performing ultrasonic oscillation at 300W of power, uniformly dispersing 2g of gamma-methacryloxypropyl trimethoxy silane coupling agent on the mixed fiber by using an atomizer, and spraying for 10min to obtain a reinforced fiber;
(4) Adding 4g 1, 2-propylene glycol, 14g neopentyl glycol, 4g phthalic acid, 14g isophthalic acid and 0.25g monobutyl tin oxide into a reaction kettle at 25 ℃, and uniformly stirring, wherein N is 2 Heating to 200 ℃ under the atmosphere, reacting for 45min, cooling to 120 ℃, adding 12g of fumaric anhydride, heating to 200 ℃ again, reacting for 45min, adding 8g of pentaerythritol triallyl ether, and carrying out end-capping reaction for 30min to obtain unsaturated polyester resin;
(5)N 2 and (2) cooling the unsaturated polyester resin to 110 ℃ in an atmosphere, sequentially adding 0.25g of hydroquinone, 4g of reinforcing fiber, 2.5g of benzoin dimethyl ether and 33g of ethoxylated trimethylolpropane triacrylate, stirring for 15min, and cooling to obtain the fiber-reinforced UV curing repair material.
The prepared repairing material is brushed on a tinplate with the size of 120mm x 50mm x 0.28mm, and the tinplate is irradiated for 3min by ultraviolet light with the wavelength of 360nm emitted by an ultraviolet lamp with the power of 800W, so that cross-linking curing is carried out. And after the solidification is finished, placing the tinplate at a drying and ventilating place, drying for more than 24 hours, and testing.
Tests prove that the volume shrinkage of the fiber-reinforced UV curing repair material after curing is 6%, the surface and actual drying time is respectively 18s and 55s, the impact strength is 20000g.cm, the flexibility is 10mm, and the adhesive force is grade 1.
Example 4
The preparation method of the fiber-reinforced UV curing repair material comprises the following steps:
(1) Washing 2.4g of carbon fiber with 5mL of absolute ethyl alcohol for 2 times at 25 ℃, then washing 3 times with 5mL of deionized water, drying for 2 hours at 90 ℃, cooling to room temperature, immersing for 3 hours with 15g of 0.5wt.% lanthanum chloride aqueous solution to obtain activated carbon fiber, immersing the activated carbon fiber in 15g of 10wt.% hydrogen peroxide aqueous solution, immersing for 5 hours, filtering, and drying for 3 hours at 120 ℃ to obtain modified carbon fiber;
(2) At the temperature of 25 ℃, 1.6g of aramid fiber is placed in a vacuum reactor, the temperature is raised to 200 ℃, the vacuum is pumped until the pressure is less than-0.07 Mpa, and the filling molar ratio is 12:1, the pressure of the mixed gas of carbon tetrachloride and ammonia gas is 0.05Mpa, and the radio-frequency electrode is under 60KV voltage, 4W/m 3 Discharging power to the reactor for 1.5h, vacuumizing to pressure less than-0.08 MPa, and charging N 2 Cooling to normal pressure to obtain modified aramid fibers;
(3) Uniformly mixing 2.4g of modified carbon fiber and 1.6g of modified aramid fiber at 25 ℃, ultrasonically oscillating at 300W, uniformly dispersing 2g of gamma-methacryloxypropyl trimethoxy silane coupling agent on the mixed fiber by using an atomizer, and spraying for 10min to obtain a reinforced fiber;
(4) At 25 ℃, 8g of 1, 2-propylene glycol, 10g of neopentyl glycol, 12g of phthalic acid, 6g of isophthalic acid and 0.25g of monobutyl tin oxide are added into a reaction kettle and stirred uniformly, and N 2 Heating to 200 deg.C under atmosphere, reacting for 45min, cooling to 120 deg.C, adding 12g fumaric anhydride, and addingHeating to 200 ℃ for the second time, reacting for 45min, adding 6g of pentaerythritol triallyl ether, and carrying out end capping reaction for 30min to obtain unsaturated polyester resin;
(5)N 2 and (2) cooling the unsaturated polyester resin to 110 ℃ in an atmosphere, sequentially adding 0.25g of hydroquinone, 3g of reinforcing fiber, 2.5g of benzoin dimethyl ether and 30g of ethoxylated trimethylolpropane triacrylate, stirring for 15min, and cooling to obtain the fiber-reinforced UV curing repair material.
The prepared repairing material is brushed on a tinplate with the size of 120mm x 50mm x 0.28mm, and the tinplate is irradiated for 3min by ultraviolet light with the wavelength of 360nm emitted by an ultraviolet lamp with the power of 800W, so that cross-linking curing is carried out. And after the solidification is finished, placing the tinplate at a drying and ventilating place, drying for more than 24 hours, and waiting for testing.
Tests prove that the volume shrinkage of the fiber-reinforced UV curing repair material after curing is 7%, the surface drying time and the actual drying time are respectively 21s and 60s, the impact strength is 16000g.cm, the flexibility is 10mm, and the adhesive force is grade 2.
Example 5
The preparation method of the fiber-reinforced UV curing repair material specifically comprises the following steps:
(1) Washing 4.5g of carbon fiber with 5mL of absolute ethyl alcohol for 2 times at 25 ℃, then washing with 5mL of deionized water for 3 times, drying for 2 hours at 90 ℃, cooling to room temperature, immersing with 15g of 0.5wt.% lanthanum chloride aqueous solution for 3 hours to obtain activated carbon fiber, immersing the activated carbon fiber in 15g of 10wt.% hydrogen peroxide aqueous solution, immersing for 5 hours, filtering, and drying at 120 ℃ for 3 hours to obtain modified carbon fiber;
(2) At the temperature of 25 ℃, 3g of aramid fiber is placed in a vacuum reactor, the temperature is raised to 200 ℃, the vacuum is pumped until the pressure is less than-0.07 Mpa, and the filling molar ratio is 12:1, the pressure of the mixed gas of carbon tetrachloride and ammonia gas is 0.05Mpa, and the radio-frequency electrode is under 60KV voltage, 4W/m 3 Discharging the reactor for 1.5h, vacuumizing to a pressure of less than-0.08 MPa, and charging N 2 Cooling to normal pressure to obtain modified aramid fibers;
(3) Uniformly mixing 4.5g of modified carbon fiber and 3g of modified aramid fiber at 25 ℃, ultrasonically oscillating at 300W, uniformly dispersing 3g of gamma-methacryloxypropyltrimethoxysilane coupling agent on the mixed fiber by using an atomizer, and spraying for 10min to obtain a reinforced fiber;
(4) Adding 9g of 1, 2-propylene glycol, 9g of neopentyl glycol, 9g of phthalic acid, 9g of isophthalic acid and 0.25g of monobutyl tin oxide into a reaction kettle at 25 ℃, and uniformly stirring the mixture, wherein N is 2 Heating to 200 ℃ under the atmosphere, reacting for 45min, cooling to 120 ℃, adding 13g of fumaric anhydride, heating to 200 ℃ again, reacting for 45min, adding 7g of pentaerythritol triallyl ether, and carrying out end-capping reaction for 30min to obtain unsaturated polyester resin;
(5)N 2 and (2) cooling the unsaturated polyester resin to 110 ℃ in an atmosphere, sequentially adding 0.25g of hydroquinone, 2.5g of reinforcing fiber, 2.5g of benzoin dimethyl ether and 30g of ethoxylated trimethylolpropane triacrylate, stirring for 15min, and cooling to obtain the fiber-reinforced UV curing repair material.
The prepared repairing material is brushed on a tinplate with the size of 120mm x 50mm x 0.28mm, and the tinplate is irradiated for 3min by ultraviolet light with the wavelength of 360nm emitted by an ultraviolet lamp with the power of 800W, so that cross-linking curing is carried out. And after the solidification is finished, placing the tinplate at a drying and ventilating place, drying for more than 24 hours, and waiting for testing.
Tests prove that the volume shrinkage of the fiber-reinforced UV curing repair material after curing is 8%, the surface drying time and the actual drying time are respectively 17s and 50s, the impact strength is 19000g.cm, the flexibility is 5mm, and the adhesive force is 0 grade.
From the performances of the final products of examples 1 to 5, the volume shrinkage of the repair material is finally affected by the density of unsaturated double bonds (the amount of the unsaturated dibasic acid) and the amount of the diluent, the volume shrinkage of the repair material after curing is increased by the excessively high density of the double bonds and the large amount of the diluent (the double bonds can open the mutual crosslinking of the double bonds to form a network structure in the curing process to change the structure of the material), and the repair material is difficult to process by the excessively low density of the double bonds and the low amount of the diluent; the use level of pentaerythritol triallyl ether serving as a resin end-capping agent can influence the drying time of the cured repair material, and if the use level is too low, the concentration of active allyl is insufficient, the effect is insufficient, and if the use level is too high, the effect cannot be fully exerted by the active allyl, so that the drying time can be prolonged; the ratio of phthalic acid to isophthalic acid in saturated dibasic acid and the addition amount of the reinforcing fiber can influence the mechanical property of the cured repair material, the impact strength is low when the ratio of phthalic acid is too high, the flexibility and the adhesive force are reduced when the ratio of isophthalic acid is too high, the addition amount of the reinforcing fiber is small, the improvement of the mechanical property is limited, the fiber is difficult to be fully fused by resin when the ratio of isophthalic acid is too high, and the mechanical property is reduced on the contrary.
Some of the criteria referred to in the examples for each performance measurement method are as follows:
(1) And (3) measuring the volume shrinkage rate of the repairing material before and after curing: according to ISO 3521-1997 standard of determination of total volume shrinkage of plastic unsaturated polyester and epoxy resin, a density method is adopted to determine the volume shrinkage of the repair material before and after ultraviolet curing.
(2) Determination of drying time of the cured repair material: the surface drying and actual drying time of the repair material are tested according to the test standard GB/T1728-1979 'determination method for drying time of lacquer putty film'.
Repair material paint films were prepared for testing on 120mm 50mm 0.28mm tin plates according to GB 1727-79 "general paint film preparation method".
(3) And (3) determination of the impact strength of the cured repair material: and (3) determining the impact strength of the cured repair material by referring to GB/T1732-1993 paint film impact resistance test method.
Repair material paint films were prepared on 120mmx 50mmx 0.28mm tin plates according to GB 1727-79 "general preparation of paint films" and tested using a paint film impact tester.
(4) And (3) measuring the flexibility of the cured repair material: the flexibility of the cured repair material is determined by means of a spindle tester, in accordance with GB/T1731-1993, paint film flexibility determination.
Repair material paint films were prepared for testing on 120mm 50mm 0.28mm tin plates according to GB 1727-79 "general paint film preparation method".
(5) And (3) determining the adhesion force of the cured repair material: referring to GB/T9286-1998 test for marking colored and clear paint films, the flexibility of the repair material after curing is determined by means of 1 mm-spaced hundred-grid knives and special test tapes.
Repair material paint films were prepared for testing on 120mmx 50mmx 0.28mm tin plates according to GB 1727-79 "general preparation of paint films".
Claims (4)
1. A fiber-reinforced UV-curable repair material, characterized in that: the repairing material is prepared from unsaturated polyester resin, reinforcing fibers, a polymerization inhibitor, a photosensitizer and a diluent according to the mass ratio of 1:0.04 to 0.07:0.004 to 0.005:0.04 to 0.05:0.5 to 0.6;
wherein the unsaturated polyester resin is prepared by the following method: carrying out polycondensation reaction on dihydric alcohol and saturated dibasic acid under the action of an organotin catalyst at high temperature in an inert gas atmosphere, adding unsaturated dibasic acid into the reaction product after the reaction, carrying out polycondensation reaction again, adding a terminating agent after the reaction, and carrying out terminating reaction to obtain unsaturated polyester resin; the dihydric alcohol is neopentyl glycol and 1, 2-propylene glycol according to the mass ratio of 1 to 3.5: 1; the saturated dibasic acid is isophthalic acid and phthalic acid according to a mass ratio of 0.5 to 3.5: 1; the unsaturated dibasic acid is fumaric anhydride; the end capping agent is pentaerythritol triallyl ether or rosin; the organic tin catalyst is monobutyl tin oxide or dibutyltin dilaurate;
the reinforcing fiber is obtained by compounding modified carbon fibers and modified aramid fibers in a mass ratio of 1 (0.6 to 0.7) under the action of a silane coupling agent; the modified carbon fiber is prepared by the following method: after being cleaned and dried, the carbon fiber is firstly soaked and activated by a rare earth salt water solution and then is prepared by oxidizing treatment by an oxidant after activation; the rare earth salt is lanthanum chloride or cerium nitrate; the oxidant is 10 to 20wt.% aqueous hydrogen peroxide solution or 5 to 10wt.% aqueous sodium hypochlorite solution;
wherein the diluent is ethoxylated trimethylolpropane triacrylate;
the modified aramid fiber is prepared by the following method: placing aramid fibers in a vacuum reactor at room temperature, heating to 200-300 ℃, vacuumizing, then filling mixed reaction gas, discharging the mixed gas by a radio-frequency electrode, performing low-temperature plasma surface treatment on the aramid fibers, vacuumizing again after the completion of the low-temperature plasma surface treatment, and filling inert gas to normal pressure to obtain the modified aramid fibers.
2. The fiber-reinforced UV-curable repair material according to claim 1, wherein: the mass ratio of the dihydric alcohol to the saturated dibasic acid to the unsaturated dibasic acid to the end-capping reagent to the organotin catalyst is 1:1 to 1.05:0.6 to 0.75:0.3 to 0.45:0.013 to 0.014.
3. The fiber-reinforced UV-curable repair material according to claim 1, wherein: the silane coupling agent is gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane or gamma-methacryloxypropyltrimethoxysilane coupling agent; the mass ratio of the silane coupling agent to the modified carbon fiber is 1.4 to 1.5.
4. The preparation method of the fiber-reinforced UV curing repair material of any one of claims 1 to 3, which is characterized by comprising the following steps: cooling the synthesized unsaturated polyester resin to 100-120 ℃ under the inert gas atmosphere, adding a polymerization inhibitor, a reinforced fiber, a photosensitizer and a diluent in a formula amount into the unsaturated polyester resin, and stirring and compounding to obtain a pipeline repairing material, namely a fiber reinforced UV curing repairing material; wherein the polymerization inhibitor is hydroquinone or p-hydroxyanisole; the photosensitizer is benzoin dimethyl ether or benzoin ethyl ether.
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