CN113817290B - Anti-shrinkage self-repairing epoxy resin/microcapsule composite material and preparation method thereof - Google Patents
Anti-shrinkage self-repairing epoxy resin/microcapsule composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-shrinkage self-repairing type epoxy resin/microcapsule composite material and a preparation method thereof, wherein the composite material comprises epoxy resin, a curing agent and an anti-shrinkage self-repairing type microcapsule; the anti-shrinkage self-repairing microcapsule is a hollow vesicle which is constructed by high polymer materials and has the size grain diameter of 100-400 mu m, and comprises a core material and a wall material; the core material comprises a polymerization monomer, an expansion monomer and a thermal light initiation system; the wall material comprises urea-formaldehyde resin doped with a thermal light shielding agent; the monomer mixture is a monomer mixture which is not shrunk in volume and has good electric insulation performance after curing, and the whole volume slightly expands after thermal light-initiated polymerization curing. The core material repairing agent slightly expands in overall volume after being cured, and has double effects of thermocuring and photocuring, so that the self-repairing efficiency is improved, and shrinkage prevention and self-repairing are performed on damage defects of the epoxy resin insulating material.
Description
Technical Field
The invention relates to the technical field of electrical insulation and composite materials, in particular to an anti-shrinkage self-repairing type epoxy resin/microcapsule composite material and a preparation method thereof.
Background
Epoxy resin materials are widely used in the field of electrical insulation because of their good electrical insulation, chemical stability, and weatherability. However, in an actual operation environment, the insulation materials such as epoxy resin and the like are affected by various factors such as electricity, humidity, heat, machinery, chemistry and the like for a long time, the materials are aged to further generate defects such as micropores and electrical dendrites, and in addition, damages such as scratches, tensile cracks and the like generated by improper operation in the transportation and assembly processes can also distort an electric field and cause phenomena such as dendritic discharge and the like, so that the insulation performance is reduced, and even serious accidents can be caused. In addition, the conventional techniques are difficult to detect and repair such minute damage or defect portions, and often require the entire apparatus to be replaced after a power failure. Therefore, the damage defect can bring great influence to the production and life of people, and can cause the waste of a large amount of insulating materials.
The microcapsule self-repairing technology is a great innovation, and is characterized in that microcapsules wrapped with a repairing agent are doped into a base material, when crack defects are generated, the microcapsules are broken under the action of tip stress, and the repairing agent flows out and is polymerized and cured under the external stimulation conditions (heat, light, a catalyst and the like) so as to repair the crack defects. However, the repairing agent is solidified by liquid through polymerization reaction, and the intermolecular distance is converted into the intramolecular distance, so that the polymer is arranged more densely than a monomer, and the phenomena of volume shrinkage and the like generally occur, so that the combination between the base material and the solidified product is not very tight, a small gap can occur again, the damage defect is not eliminated, and the integrity and the mechanical strength of the composite material are influenced.
In the existing research on microcapsule self-repairing, researchers generally select core materials with good mechanical properties or electrical properties after curing, and do not pay attention to the problem of volume shrinkage.
The prior Chinese patent application CN109294166A of the same applicant discloses an epoxy resin composite insulating material and a preparation method thereof, wherein a repairing agent selects dicyclopentadiene, and when damage defects occur, the repairing agent flows out and contacts Grubbs catalyst doped in the epoxy resin composite insulating material to react to repair the defects, so that the self-repairing function of the epoxy resin is realized. In this prior art, dicyclopentadiene as a repair agent undergoes volume shrinkage upon curing, resulting in a small gap between the substrate and the cured product, and the defect of damage is not completely eliminated.
Disclosure of Invention
In order to optimize the existing self-repairing technology, the invention aims to provide an anti-shrinkage self-repairing type epoxy resin/microcapsule composite material and a preparation method thereof, by means of the microcapsule self-repairing technology, a polymerized monomer benzoxazine mixed expansion monomer is used as a repairing agent, the benzoxazine monomer is cured by thermal stimulation, the mechanical property and the electrical property of a cured product are good, and the cured product is not shrunk basically; the expandable monomer is cured by light stimulation, and the volume expands after curing. Therefore, the whole volume of the core material repairing agent slightly expands after being cured, the core material repairing agent has double effects of thermocuring and photocuring, external stimulation conditions are fully utilized, the self-repairing efficiency is improved, shrinkage prevention and self-repairing are carried out on damage defects of the epoxy resin insulating material, and the problem of curing shrinkage of a common repairing agent is solved.
The invention adopts the following technical scheme:
an anti-shrinkage self-repairing type epoxy resin/microcapsule composite material comprises epoxy resin, a curing agent and anti-shrinkage self-repairing type microcapsules;
the anti-shrinkage self-repairing microcapsule comprises a core material and a wall material; the shrinkage-proof self-repairing microcapsule is cured by thermal light initiation, and a repairing agent monomer with slightly expanded volume after curing is taken as a core material.
Preferably, the core material comprises a polymeric monomer, an intumescent monomer and a thermo-photoinitiating system; the wall material comprises urea-formaldehyde resin doped with a thermal light shielding agent;
the method adopts a polymerization monomer mixed expansion monomer which has no volume shrinkage after curing and good electrical insulation performance, and the whole volume slightly expands after thermal light initiated polymerization curing.
Preferably, the polymeric monomer is benzoxazine.
Preferably, the swelling monomer is a cyclic compound which undergoes volume expansion after polymerization, and ring-opening stretching polymerization causes volume expansion.
Preferably, the expansion monomer is one or more of spiro orthocarbonate, spiro orthoester, bicyclo orthoester and bicyclo lactone expansion monomers.
Preferably, the spirocyclic orthocarbonate swelling monomer comprises 3, 9-diethyl-3, 9-bis (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane.
Preferably, the polymerized monomer is cured by thermal stimulation, and the volume is not shrunk after curing; the expansion monomer is cured by light stimulation, and the volume of the cured expansion monomer expands.
Preferably, the thermal photoinitiating system comprises a thermal initiator and a photoinitiating system.
Preferably, the thermal initiator is at least one of diphenyliodonium hexafluorophosphate, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers.
Preferably, the photoinitiation system comprises a photoinitiator, a photosensitizer and a sensitizing agent;
the photoinitiator is a cationic photoinitiator, the photosensitizer is a free radical photosensitizer, and the sensitizer is an electron donor compound.
Preferably, the photoinitiator is at least one of diphenyl iodonium hexafluorophosphate, diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxy ether;
the photosensitizer is at least one of benzil, benzoin and derivatives thereof, acetophenone derivatives, aromatic ketone compounds, acyl phosphine oxides and the like;
the sensitization promoter is N, N-dimethylamino ethyl methacrylate.
Preferably, both the thermal initiator and the photoinitiator are diphenyliodonium hexafluorophosphate.
Preferably, in the core material, the ratio of polymerized monomer: an expansion monomer: thermal initiator: photoinitiator (2): photosensitizer: the weight ratio of the sensitizing agent is 100.
Preferably, in the anti-shrinkage self-repairing microcapsule, the weight ratio of the wall material to the core material is 3:10, wall thickness 4 μm.
Preferably, in the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material, the epoxy resin accounts for 90-110 parts by weight, the curing agent accounts for 27-33 parts by weight, and the anti-shrinkage self-repairing type microcapsule accounts for 3.6-4.4 parts by weight.
Preferably, in the shrinkage-proof self-repairing epoxy resin/microcapsule composite material, the ratio of epoxy resin: curing agent: the weight ratio of the anti-shrinkage self-repairing microcapsule is 100:30:4 parts by weight.
Preferably, the wall material of the microcapsule comprises urea formaldehyde resin, and is doped with a thermal light shielding agent.
A method for preparing the anti-shrinkage self-repairing epoxy resin/microcapsule composite material, which comprises the following steps:
step 1, preparing an expansion monomer;
step 2, blending a polymerization monomer, an expansion monomer and a thermo-photo initiation system to be used as a core material, and using urea resin doped with a thermo-photo shielding agent as a wall material to prepare the shrinkage-proof self-repairing microcapsule;
and 3, mixing the epoxy resin, the curing agent and the anti-shrinkage self-repairing type microcapsule prepared in the step 2, and curing to form the epoxy resin/microcapsule anti-shrinkage self-repairing type composite material.
Preferably, in step 1, trimethylolpropane monoallyl ether and tetraethyl orthocarbonate are reacted to produce the swelling monomer 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane, which specifically includes:
step 1.1, adding a solvent into anhydrous sodium carbonate and p-toluenesulfonic acid, and then adding reactants trimethylolpropane monoallyl ether and tetraethyl orthocarbonate to fully react;
and step 1.2, decompressing and concentrating a product obtained by the reaction, and separating and purifying by column chromatography to obtain the expansion monomer.
20. The method according to claim 19,
the step 2 comprises the following steps:
step 2.1, urea and formaldehyde are used for preparing a urea-formaldehyde resin prepolymer;
step 2.2, adding a polymerization monomer, an expansion monomer and a thermal light initiation system into a nano titanium dioxide aqueous solution, and emulsifying into an oil-in-water emulsion;
and 2.3, adding the prepolymer in the step 2.1 into the emulsion in the step 2.2, and simultaneously adding a curing agent to prepare the anti-shrinkage self-repairing microcapsule.
Compared with the prior art, the shrinkage-proof self-repairing epoxy resin/microcapsule composite material has the beneficial effects that when damage defects such as cracks, electric branches and the like occur in an insulating material, the microcapsules are broken due to tip stress, core materials (benzoxazine and expansion monomers) flow out, and the core materials are cured by double actions of thermal curing and photocuring at about 130 ℃ due to the heating and luminescence phenomena occurring in the branch discharging process, so that the curing efficiency is improved, and the volume of the core materials slightly expands after being cured, so that the shrinkage-proof self-repairing is performed on the damage defects of the insulating material, and the defect of curing shrinkage of common core materials is overcome.
Drawings
FIG. 1 is a process diagram of the preparation method of the shrinkage-proof self-repairing epoxy resin/microcapsule composite material of the present invention.
Detailed Description
The present application is further described below with reference to the accompanying drawings. The following examples are only used to illustrate the technical solutions of the present invention more clearly, and the protection scope of the present application is not limited thereby.
The shrinkage-proof self-repairing epoxy resin/microcapsule composite material is prepared by uniformly blending epoxy resin, a curing agent and a shrinkage-proof self-repairing microcapsule according to a certain mass ratio and curing to form the shrinkage-proof self-repairing epoxy resin/microcapsule composite material.
The microcapsule is a hollow vesicle which is constructed by high polymer materials and has the particle size of 100-400 mu m, and the microcapsule takes a repairing agent monomer which can be cured by heat and light and slightly expands in volume after being cured as a core material and takes urea-formaldehyde resin as a wall material. The anti-shrinkage self-repairing microcapsule comprises a core material and a wall material, wherein the core material comprises a polymerization monomer, an expansion monomer and a thermo-photo initiation system, and the wall material comprises urea formaldehyde resin doped with a thermo-photo shielding agent.
The core material of the microcapsule comprises a polymerization monomer, an expansion monomer and a thermal light initiation system, wherein the polymerization monomer which is not shrunk in volume and has good electric insulation performance after curing is mixed with the expansion monomer, and the whole volume slightly expands after thermal light initiation polymerization curing. The polymerized monomer is preferably benzoxazine which is a novel thermosetting resin, and the curing shrinkage is almost zero because no micromolecules are released in the curing process, the modulus is high, the strength is high, the heat resistance is good, and the electric insulation performance is good.
The swelling monomer is selected from cyclic compounds which swell in volume after polymerization, and is subjected to ring-opening stretching polymerization to cause volume swelling, and preferably swelling monomers such as spiro orthocarbonate, spiro orthoester, bicyclo orthoester, and bicyclo cyclic lactone are used. Spiro orthocarbonate type swelling monomers such as 3, 9-diethyl-3, 9-bis (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane can be cured by photopolymerization by irradiation with light such as ultraviolet light in the presence of a photoinitiating system, and the swelling monomers can undergo ring-opening polymerization with an increase in the distance between molecules, resulting in volume expansion. The reaction mechanism of the ring-opening expansion polymerization of the expansion monomer is as follows:
in fact, no polymerized monomer which expands in volume and has good electrical property after being cured is found, and the purpose of self-repairing is to achieve slight expansion on the premise of no shrinkage, so that the crack repairing effect is better. The benzoxazine has good electrical insulation performance after being cured and does not shrink, and an expansion monomer is added on the basis to expand the volume. And the properties of the cured products of the two monomers can complement each other. Other expansion monomers can be selected, and the expansion principles of the monomers are basically the same, and the monomers are all in a ring structure, and the ring is opened and stretched to form a polymer, so that the volume expansion is caused.
The polymerized monomer is cured by thermal stimulation, the volume is not shrunk after curing, and the mechanical property and the electric insulation property of the cured product are good. The expansion monomer is cured by light stimulation, the volume of the cured monomer is expanded, and the elastic property of the cured product is good. The combination of the two substances causes the curing volume to slightly expand, and the shrinkage prevention and self repair can be carried out on the damage defect. Meanwhile, the performances of the two cured products can be mutually complemented, and the tensile property of the epoxy resin composition is improved on the basis of ensuring good mechanical property and electrical insulation property. And one is thermal stimulation solidification and the other is light stimulation solidification, and the two solidification modes are not in conflict, so that the external stimulation condition is fully utilized, and the solidification efficiency is improved.
The thermal photoinitiation system includes a thermal initiator and a photoinitiation system. The thermal initiator is an initiator which can reduce the curing temperature of the benzoxazine to a temperature at which partial discharge can reach, such as at least one of diphenyliodonium hexafluorophosphate, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketone and triarylsiloxy ether. The photoinitiation system comprises a photoinitiator, a photosensitizer and a sensitizing agent. In the process of partial discharge, heat and light can be generated, but the light is weak, and in order to promote photocuring, a photosensitizer and a sensitizer are added on the basis of an initiator to promote photocuring. The photoinitiator absorbs energy with certain wavelength under the action of light to generate cations, so that the polymerization and curing of the monomer are initiated. And the photosensitizer and the sensitizing agent are used for promoting the photoinitiator to absorb energy to generate cations so as to promote the polymerization and curing of the monomer. The photoinitiator is cationic photoinitiator, such as at least one of diphenyl iodonium hexafluorophosphate, diaryl iodonium salt, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxy ether; the photosensitizer is free radical photosensitizer, such as at least one of benzil, benzoin and derivatives thereof, acetophenone derivatives, aromatic ketone compounds, acyl phosphine oxide, etc.; the sensitization promoter is electron donor compound such as N, N-dimethylamino ethyl methacrylate. Preferably, diphenyl iodonium hexafluorophosphate is selected as a thermal initiator and a photoinitiator simultaneously, so that the curing temperature of benzoxazine can be reduced, the diphenyl iodonium hexafluorophosphate can be used as the thermal initiator of benzoxazine, and the diphenyl iodonium hexafluorophosphate is also used as the photoinitiator, so that the initiator types can be reduced.
That is, the core material includes a polymerization monomer, an expansion monomer, a thermal initiator, a photoinitiator, a photosensitizer, and a sensitizer. The weight ratio of each component is as follows: an expansion monomer: thermal initiator: photoinitiator (2): photosensitizer: sensitizer = 100. In one embodiment of the invention, the thermal initiator and the photoinitiator may be chosen from the same material. The polymerized monomer is selected from benzoxazine; the expansion monomer is 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane; the thermal initiator and the photoinitiator are diphenyl iodonium hexafluorophosphate, the photosensitizer is benzil, and the sensitization promoter is N, N-dimethylamino ethyl methacrylate. The weight ratio of the components is as follows: 3, 9-diethyl-3, 9-bis (allyloxymethyl) -1,5,7, 11-tetraoxaspiro [5,5] undecane: diphenyliodonium hexafluorophosphate: benzil: n, N-dimethylamino ethyl methacrylate =100:30:6.5:0.5:0.05.
the wall material of the microcapsule comprises urea resin and is doped with a thermal light shielding agent. The thermo-optical shielding agent adopts at least one of nano titanium dioxide, vitrified micro bubbles, ceramic micro bubbles and the like which can shield heat and light.
In the anti-shrinkage self-repairing microcapsule, the weight ratio of the wall material to the core material is about 3:10, the wall thickness is about 4 mu m, so that the microcapsules can be wrapped by enough core materials, certain mechanical properties of the microcapsules can be guaranteed, the integrity of the microcapsules can be kept before self-repairing action, and the microcapsules can be broken in time to trigger the self-repairing action when damage is generated.
In the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material, 90-110 parts by weight of base material epoxy resin, 27-33 parts by weight of curing agent, 3.6-4.4 parts by weight of microcapsule, preferably 100:30:4 parts by weight. The microcapsule which accounts for about 4 percent of the epoxy resin material of the base material can furthest realize the self-repairing performance on the basis of ensuring the good electrical insulating performance of the composite material. Epon-828 is preferably used as the epoxy, although other thermoset insulating materials may be used. The curing agent is at least one of epoxy resin curing agent 593 or other aliphatic amine, alicyclic amine, aromatic amine, polyamide, acid anhydride, resin epoxy resin curing agent, etc.
According to the shrinkage-proof self-repairing epoxy resin/microcapsule composite material, when damage defects such as cracks, electric branches and the like occur in the insulating material, the microcapsules are broken due to tip stress, the core material flows out, heating and light emitting phenomena can occur in the partial discharge process, the core material is cured at about 130 ℃ through double effects of thermal curing and light curing, the curing efficiency is improved, and the core material expands in volume after being cured, so that shrinkage-proof self repairing is performed on the damage defects of the insulating material, and the defect of curing shrinkage of a common repairing agent is overcome. In addition, the two cured products complement each other in performance, and the repairing effect is better.
The shrinkage-resistant self-repairing epoxy resin/microcapsule composite material is prepared by the following method:
step 1, trimethylolpropane monoallyl ether and tetraethyl orthocarbonate were used as reactants to prepare the swelling monomer 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane. The other 1,5,7,11 tetraoxaspiro [5,5] undecane swelling monomers were prepared in a similar principle, except that the side chains differed resulting in different reactants.
Further, in step 1, trimethylolpropane monoallyl ether and tetraethyl orthocarbonate were reacted in the presence of sodium carbonate and p-toluenesulfonic acid to prepare the swelling monomer 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane.
More specifically, step 1 comprises:
step 1.1, adding a solvent into anhydrous sodium carbonate and p-toluenesulfonic acid, and then adding reactants trimethylolpropane monoallyl ether and tetraethyl orthocarbonate to fully react.
The reaction formula of the reactants is
Preferably, the solvent is at least one of tetrahydrofuran, toluene, diethyl ether and the like; the weak base condition can be at least one selected from sodium carbonate, sodium bicarbonate, sodium acetate, etc.
The trimethylolpropane monoallyl ether is 11.25-13.75 parts by weight of analytical purity grade; the tetraethyl orthocarbonate is 4.14-5.06 parts by weight of analytical grade; the adopted solvent is anhydrous and oxygen-free; the anhydrous sodium carbonate is in an analytically pure grade of 6.867 to 8.393 parts by weight; 0.747-0.913 parts by weight of p-toluenesulfonic acid by weight of an analytical grade; the reaction time is 11-13h; the reaction environment is anhydrous and anaerobic and is ice-bath, and the magnetic stirring speed is 450-550rpm.
And step 1.2, decompressing and concentrating a product obtained by the reaction, and separating and purifying by column chromatography to obtain the expansion monomer.
Preferably, in the case of column chromatography, the eluent is petroleum ether: ethyl acetate =20:1 weight ratio.
And 2, blending the polymerized monomer, the expanded monomer and the thermal light initiation system to be used as a core material, and using the urea-formaldehyde resin doped with the shielding agent as a wall material to prepare the shrinkage-proof self-repairing microcapsule.
And 2.1, preparing a urea-formaldehyde resin prepolymer by using urea and formaldehyde.
Specifically, urea is taken and dissolved in deionized water, formaldehyde is added, triethanolamine is used for adjusting the pH value to be 8-9, the solution is heated to 70-73 ℃, and the reaction is carried out for 1 hour under the condition of magnetic stirring at 400rpm, so as to obtain colorless and transparent urea-formaldehyde resin prepolymer for later use.
The urea accounts for 4.689-5.731 parts by weight of analytically pure, the formaldehyde accounts for 10.8-13.2 parts by weight of analytically pure with 35% concentration, the reaction conditions are that the pH is = 8-9, the temperature is 70-73 ℃, the magnetic stirring is carried out at 400rpm, and the reaction time is 1 hour.
And 2.2, adding the polymerization monomer, the expansion monomer and the thermal light initiation system into the nano titanium dioxide aqueous solution, and emulsifying into an oil-in-water emulsion.
Specifically, the nano titanium dioxide is added into deionized water, then polyethylene glycol aqueous solution is added into the deionized water, and the nano titanium dioxide is fully dispersed in the aqueous solution under ultrasonic equipment. Then, a polymerization monomer such as benzoxazine, an expansion monomer, a thermo-photo initiation system as a core material repair agent was slowly added thereto, and emulsified for 30 minutes to form a stable oil-in-water emulsion.
The nano titanium dioxide is 0.63-0.77 parts by weight of analytically pure, and the polyethylene glycol is 2wt% of 1.8-2.2 parts by weight of analytically pure.
In the core material repairing agent, the polymeric monomer is benzoxazine; the expansion monomer is 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane; the thermal initiator and the photoinitiator are both diphenyl iodonium hexafluorophosphate, the photosensitizer is benzil, and the sensitizer is N, N-dimethylamino ethyl methacrylate. The weight ratio of the components is that benzoxazine: an expansion monomer: diphenyliodonium hexafluorophosphate: benzil: n, N-dimethylamino ethyl methacrylate =100:30:6.5:0.5:0.05.
and 2.3, adding the prepolymer obtained in the step 2.1 into the emulsion obtained in the step 2.2, and adding a curing agent to prepare the anti-shrinkage self-repairing microcapsule.
Specifically, the prepolymer prepared in step 2.1 is added into the emulsion, and the curing agent is added at the same time, dilute hydrochloric acid is adopted to slowly adjust the pH of the solution to be about =3.5, the temperature is gradually increased to 60-65 ℃, and the reaction is carried out for 3 hours. And carrying out suction filtration, washing and drying to obtain microcapsule powder. Removing scraps by a sieve, and screening out the microcapsules with uniform particle size of 100-400 mu m.
9-11 parts of core material repairing liquid; the prepolymer is 18-22 parts by weight, the curing agent is 0.36-0.44 part by weight of resorcinol, and the ammonium chloride is 0.27-0.33 part by weight; the reaction conditions are about pH3.5, the temperature is 60-65 ℃, and the reaction time is 3 hours. The microcapsules are filtered, washed, dried and screened to obtain microcapsules with uniform particle sizes of 100-400 mu m.
And 3, mixing epoxy resin, a curing agent and the anti-shrinkage self-repairing type microcapsule prepared in the step 2, and curing to form the epoxy resin/microcapsule anti-shrinkage self-repairing type composite material.
Specifically, the epoxy resin accounts for 90-110 parts by weight, the curing agent accounts for 27-33 parts by weight, and the microcapsule accounts for 3.6-4.4 parts by weight, preferably 100:30:4 parts by weight. Epon-828 is preferred as the epoxy resin, and 593 is preferred as the curing agent. The microcapsule which accounts for about 4 percent of the matrix material can realize the self-repairing performance to the maximum extent on the basis of ensuring the good electrical insulating performance of the composite material.
The epoxy resin, the curing agent and the microcapsule are fully and uniformly mixed according to a certain mass ratio, the mixture is vacuumized at 50 ℃ for about 10min, and the mixture is cured and formed at 40 ℃ to prepare the shrinkage-proof self-repairing type epoxy resin/microcapsule composite material.
The invention selects the benzoxazine mixed expansion monomer as the core material of the self-repairing microcapsule. The core material can slightly expand in volume after being cured, and the defect of shrinkage of the cured volume of a common core material is overcome. Meanwhile, benzoxazine is cured by thermal stimulation, the expansion monomer is cured by light stimulation, and the combination of thermal stimulation and light stimulation can fully utilize external stimulation conditions and improve the curing efficiency. Also, the two cured product properties can complement each other.
In order to more clearly describe the present invention, specific embodiments of the present invention are further described below.
Example 1
Step 1, preparing an expansion monomer:
6.867g of anhydrous sodium carbonate solid and 0.747g of p-toluenesulfonic acid were weighed and charged in a 100ml flask, and 40ml of tetrahydrofuran solvent was added, followed by addition of 11.25g of trimethylolpropane monoallyl ether and 4.14g of tetraethyl orthocarbonate, and the mixture was reacted for 11 hours under magnetic stirring in an ice bath at 450rpm to allow complete reaction. The product was concentrated under reduced pressure and purified by column chromatography (petroleum ether: ethyl acetate = 20).
Step 2, preparing microcapsules:
dissolving 4.689g of urea into 40ml of deionized water, adding 10.8g of formaldehyde, adjusting the pH to 8-9 by using triethanolamine, heating the solution to 70-73 ℃, and reacting for 1 hour under the condition of magnetic stirring at 360rpm to obtain a colorless and transparent urea-formaldehyde resin prepolymer for later use;
0.63g of nano titanium dioxide is added into 50ml of deionized water, 1.8ml of 2wt% polyethylene glycol aqueous solution is added into the deionized water, ultrasonic treatment is carried out for 9 minutes under 500W of ultrasonic equipment, so that the nano titanium dioxide is fully dispersed in the aqueous solution, and then 50ml of deionized water is added for dilution. It was poured into a flask and kept at a constant temperature of 40 ℃.
Under stirring, 9g of core repair liquid (benzoxazine: swelling monomer: diphenyliodonium hexafluorophosphate: benzil: N, N-dimethylamino ethyl methacrylate = 100) was slowly added to it to emulsify to form a stable oil-in-water emulsion. Then, 18g of prepolymer and 0.36g of resorcinol were added thereto, 0.27g of ammonium chloride was gradually added in portions, and finally, the system pH =3.5 was adjusted with dilute hydrochloric acid, and the temperature was gradually increased to 65 ℃ during the reaction for 3 hours. The microcapsule powder is obtained by means of suction filtration, washing, drying and the like. Removing scraps by a sieve, and screening out the microcapsules with uniform particle size of 100-400 mu m.
Step 3, preparing the epoxy resin/microcapsule composite material:
fully and uniformly mixing 90 parts of epoxy resin Epon-828, 27 parts of epoxy resin curing agent 593 and 3.6 parts of microcapsule, vacuumizing for 9min at 50 ℃, pouring the mixed raw materials into a mould, and curing for 1 day at 40 ℃ to prepare the shrinkage-resistant self-repairing type epoxy resin/microcapsule composite material.
Example 2
Step 1, preparing an expansion monomer:
7.63g of anhydrous sodium carbonate solid and 0.83g of p-toluenesulfonic acid were weighed out and charged in a 100ml flask, and 40ml of tetrahydrofuran solvent was added, followed by addition of 12.5g of trimethylolpropane monoallyl ether and 4.6g of tetraethyl orthocarbonate, and the mixture was reacted for 12 hours under magnetic stirring at 500rpm in an ice bath to sufficiently react. The product was concentrated under reduced pressure and purified by column chromatography (petroleum ether: ethyl acetate = 20).
Step 2, preparing microcapsules:
dissolving 5.21g of urea into 40ml of deionized water, adding 12g of formaldehyde, adjusting the pH to 8-9 by using triethanolamine, heating the solution to 70-73 ℃, and reacting for 1 hour under the condition of magnetic stirring at 400rpm to obtain a colorless and transparent urea-formaldehyde resin prepolymer for later use;
0.7g of nano titanium dioxide is added into 50ml of deionized water, 2ml of 2wt% polyethylene glycol aqueous solution is added into the deionized water, ultrasonic treatment is carried out for 10 minutes under 500W of ultrasonic equipment, so that the nano titanium dioxide is fully dispersed in the aqueous solution, and then 50ml of deionized water is added for dilution. It was poured into a flask and kept at a constant temperature of 40 ℃.
10g of core repair liquid (benzoxazine: swelling monomer: diphenyliodonium hexafluorophosphate: benzil: N, N-dimethylamino ethyl methacrylate = 100) was slowly added thereto under stirring to emulsify into a stable oil-in-water emulsion. Then 20g of prepolymer and 0.4g of resorcinol were added, 0.3g of ammonium chloride was gradually added in portions, and finally the system pH =3.5 was adjusted with dilute hydrochloric acid, during which the temperature was gradually raised to 65 ℃, and the reaction was carried out for 3 hours. The microcapsule powder is obtained by means of suction filtration, washing, drying and the like. Removing scraps through a sieve, and screening out microcapsules with uniform particle size of 100-400 mu m.
Step 3, preparing the epoxy resin/microcapsule composite material:
100 parts of epoxy resin Epon-828, 30 parts of epoxy resin curing agent 593 and 4 parts of microcapsules are fully and uniformly mixed, vacuumized at 50 ℃ for 10min, and then poured into a mold for curing at 40 ℃ for 2 days for molding, so as to prepare the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material.
Example 3
Step 1, preparation of an expansion monomer:
8.393g of anhydrous sodium carbonate solid and 0.913g of p-toluenesulfonic acid were weighed into a 100ml flask, 40ml of tetrahydrofuran solvent was added, followed by 13.75g of trimethylolpropane monoallyl ether and 5.06g of tetraethyl orthocarbonate, and the mixture was reacted for 13 hours under magnetic stirring at 550rpm in an ice bath to react sufficiently. The product was concentrated under reduced pressure and purified by column chromatography (petroleum ether: ethyl acetate = 20).
Step 2, preparing microcapsules:
dissolving 5.731g urea in 40ml deionized water, adding 13.2g formaldehyde, adjusting pH to 8-9 with triethanolamine, heating the solution to 70-73 ℃, and reacting for 1 hour under the condition of magnetic stirring at 440rpm to obtain a colorless and transparent urea-formaldehyde resin prepolymer for later use;
0.77g of nano titanium dioxide is added into 50ml of deionized water, 2.2ml of 2wt% polyethylene glycol aqueous solution is added into the solution, ultrasonic treatment is carried out for 11 minutes under 500W ultrasonic equipment, so that the nano titanium dioxide is fully dispersed in the aqueous solution, and then 50ml of deionized water is added for dilution. It was poured into a flask and kept at a constant temperature of 40 ℃. To this was slowly added 11g of core repair solution (benzoxazine: swelling monomer: diphenyliodonium hexafluorophosphate: benzil: N, N-dimethylamino ethyl methacrylate = 100) under stirring to emulsify into a stable oil-in-water emulsion. Then, 22g of prepolymer and 0.44g of resorcinol were added thereto, 0.33g of ammonium chloride was gradually added in portions, and finally, the system pH =3.5 was adjusted with dilute hydrochloric acid, and the temperature was gradually increased to 65 ℃ during the reaction for 3 hours. The microcapsule powder is obtained by means of suction filtration, washing, drying and the like. Removing scraps by a sieve, and screening out the microcapsules with uniform particle size of 100-400 mu m.
Step 3, preparing the epoxy resin/microcapsule composite material:
and (2) fully and uniformly mixing 110 parts of epoxy resin Epon-828, 33 parts of epoxy resin curing agent 593 and 4.4 parts of microcapsule, vacuumizing for 11min at 50 ℃, pouring the mixed raw materials into a mould, and curing for 3 days at 40 ℃ to form the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material.
In the process of generating cracks and electric tree damage, the tip stress causes the microcapsules to break, the core material flows out, phenomena of heating, luminescence and the like can occur in the process of partial discharge, benzoxazine can be subjected to polymerization and thermosetting at 130 ℃ under the action of diphenyliodonium hexafluorophosphate, and an expansion monomer is subjected to polymerization and photocuring through ultraviolet irradiation in the presence of a diphenyliodonium hexafluorophosphate photoinitiator system, so that the damage defect is repaired. In the process, the benzoxazine is polymerized and cured in a constant volume, the expansion monomer is polymerized and cured in a volume expansion manner, and the whole volume is expanded.
An expansion/shrinkage test experiment proves that the curing shrinkage of the benzoxazine is basically 0%, the expansion rate of the expansion monomer is 7%, and the curing volume expansion of the repairing agent is about 1.6% under the conditions that the mass ratio of the benzoxazine to the expansion monomer is 100.
The expansion/shrinkage test was as follows:
preparing three centrifuge tubes, adding benzoxazine and diphenyl iodonium hexafluorophosphate accounting for 5wt% of the benzoxazine into the first centrifuge tube, and curing for 2h at 130 ℃; adding an expansion monomer (3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane), 5wt% of photoinitiator diphenyl iodonium hexafluorophosphate, 1.6wt% of photosensitizer benzil and 0.16wt% of sensitizer N, N-dimethylamino ethyl methacrylate into a second centrifugal tube, and irradiating the mixture for 2 hours by ultraviolet light at 130 ℃; and adding benzoxazine and an expansion monomer (10). Wherein, the weight ratio in the section is the proportion of the weight of the added core material.
In the formula V 0 、d 0 Volume, density, V before curing 1 、d 1 Volume and density after curing.
The benzoxazine cure shrinkage was about 0% calculated by density or volume before and after curing, the expansion monomer (3, 9-diethyl-3, 9-bis (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane) cured expansion was 7%, the benzoxazine and expansion monomer 10:3 the cure expansion after mixing was about 1.6%.
Compared with the prior art, the shrinkage-proof self-repairing type epoxy resin/microcapsule composite material has the advantages that when damage defects such as cracks and electric branches occur in an insulating material, the microcapsules break due to tip stress, core materials (benzoxazine and expansion monomers) flow out, the core materials are cured through double effects of thermal curing and photo-curing due to heating and luminescence phenomena occurring in the branch discharging process at about 130 ℃, the curing efficiency is improved, and the volume of the cured core materials slightly expands, so that the shrinkage-proof self-repairing is performed on the damage defects of the insulating material, and the defect of curing shrinkage of common core materials is overcome.
The present applicant has described and illustrated embodiments of the present invention in detail with reference to the accompanying drawings, but it should be understood by those skilled in the art that the above embodiments are only preferred embodiments of the present invention, and the detailed description is only for the purpose of helping the reader to better understand the spirit of the present invention, and not for the purpose of limiting the scope of the present invention, and on the contrary, any modifications or modifications based on the spirit of the present invention should fall within the scope of the present invention.
Claims (18)
1. An anti-shrinkage self-repairing type epoxy resin/microcapsule composite material is characterized in that,
the composite material comprises epoxy resin, a curing agent and an anti-shrinkage self-repairing microcapsule;
the anti-shrinkage self-repairing microcapsule comprises a core material and a wall material; the shrinkage-proof self-repairing microcapsule is cured by thermal light initiation, and a repairing agent monomer with slightly expanded volume after curing is taken as a core material;
the core material comprises a polymerization monomer, an expansion monomer and a thermal photo-initiation system; the wall material comprises urea-formaldehyde resin doped with a thermal light shielding agent;
the method adopts a polymerization monomer mixed expansion monomer which has no volume shrinkage after curing and good electrical insulation performance, and the whole volume slightly expands after thermal light initiated polymerization curing.
2. The shrink-resistant self-repairing epoxy resin/microcapsule composite of claim 1,
the polymerized monomer is benzoxazine.
3. The shrink-resistant self-repairing epoxy resin/microcapsule composite of claim 1,
the swelling monomer is a cyclic compound which undergoes volume expansion after polymerization, and ring-opening stretching polymerization causes volume expansion.
4. The shrink-resistant self-healing epoxy/microcapsule composite of claim 3,
the expansion monomer is one or more of spiro orthocarbonate, spiro orthoester, bicyclo orthoester and bicyclo lactone expansion monomers.
5. The shrink-resistant self-healing epoxy/microcapsule composite of claim 4,
the spiro orthocarbonate expansion monomer comprises 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7, 11-tetraoxaspiro [5,5] undecane.
6. The shrinkage-resistant self-healing epoxy/microcapsule composite of claim 1,
the polymerized monomer is cured by thermal stimulation, and the volume of the cured polymerized monomer is not shrunk; the expansion monomer is cured by light stimulation, and the volume of the cured expansion monomer expands.
7. The shrinkage-resistant self-healing epoxy/microcapsule composite of claim 1,
the thermal photoinitiation system comprises a thermal initiator and a photoinitiation system.
8. The shrink-resistant self-healing epoxy/microcapsule composite of claim 7,
the thermal initiator is at least one of diphenyl iodonium hexafluorophosphate, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxy ether.
9. The shrink-resistant self-healing epoxy/microcapsule composite of claim 7,
the photoinitiation system comprises a photoinitiator, a photosensitizer and a sensitizing agent;
the photoinitiator is a cationic photoinitiator, the photosensitizer is a free radical photosensitizer, and the sensitizer is an electron donor compound.
10. The shrinkage-resistant self-healing epoxy/microcapsule composite of claim 9,
the photoinitiator is at least one of diphenyl iodonium hexafluorophosphate, triaryl sulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone and triaryl siloxy ether;
the photosensitizer is at least one of benzil, benzoin and derivatives thereof, aromatic ketone compounds and acyl phosphine oxide;
the sensitization promoter is N, N-dimethylamino ethyl methacrylate.
11. The shrinkage-resistant self-healing epoxy/microcapsule composite of claim 9,
the thermal initiator and the photoinitiator are both diphenyl iodonium hexafluorophosphate.
12. The shrinkage-resistant self-healing epoxy/microcapsule composite of claim 9,
in the core material, a polymerized monomer: an expansion monomer: thermal initiator: photoinitiator (2): a photosensitizer: the weight ratio of the sensitizing agent is 100.
13. The shrink-resistant self-repairing epoxy resin/microcapsule composite of claim 1,
in the anti-shrinkage self-repairing microcapsule, the weight ratio of a wall material to a core material is 3:10, wall thickness 4 μm.
14. The shrink-resistant self-repairing epoxy resin/microcapsule composite of claim 1,
in the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material, 90-110 parts by weight of epoxy resin, 27-33 parts by weight of curing agent and 3.6-4.4 parts by weight of anti-shrinkage self-repairing type microcapsule are used.
15. The shrink-resistant self-healing epoxy/microcapsule composite of claim 14,
in the anti-shrinkage self-repairing type epoxy resin/microcapsule composite material, the epoxy resin: curing agent: the weight ratio of the anti-shrinkage self-repairing microcapsule is 100:30:4 parts by weight.
16. A method of preparing a shrink-resistant self-healing epoxy/microcapsule composite as claimed in any one of claims 1 to 15, comprising:
step 1, preparing an expansion monomer;
step 2, blending a polymerization monomer, an expansion monomer and a thermo-photo initiation system to be used as a core material, and using urea resin doped with a thermo-photo shielding agent as a wall material to prepare the shrinkage-proof self-repairing microcapsule;
and 3, mixing the epoxy resin, the curing agent and the anti-shrinkage self-repairing type microcapsule prepared in the step 2, and curing to form the epoxy resin/microcapsule anti-shrinkage self-repairing type composite material.
17. The method according to claim 16,
in step 1, trimethylolpropane monoallyl ether and tetraethyl orthocarbonate are used as reactants to prepare an expansion monomer 3, 9-diethyl-3, 9-di (allyloxymethyl) -1,5,7,11 tetraoxaspiro [5,5] undecane, which specifically comprises:
step 1.1, adding a solvent into anhydrous sodium carbonate and p-toluenesulfonic acid, and then adding reactants trimethylolpropane monoallyl ether and tetraethyl orthocarbonate to fully react;
and step 1.2, decompressing and concentrating a product obtained by the reaction, and separating and purifying by column chromatography to obtain the expansion monomer.
18. The method of claim 17,
the step 2 comprises the following steps:
step 2.1, urea and formaldehyde are used for preparing urea-formaldehyde resin prepolymer;
step 2.2, adding a polymerization monomer, an expansion monomer and a thermal light initiation system into the nano titanium dioxide aqueous solution, and emulsifying into an oil-in-water emulsion;
and 2.3, adding the prepolymer obtained in the step 2.1 into the emulsion obtained in the step 2.2, and adding a curing agent to prepare the anti-shrinkage self-repairing microcapsule.
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