CN116041910B - High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof - Google Patents
High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof Download PDFInfo
- Publication number
- CN116041910B CN116041910B CN202310165908.7A CN202310165908A CN116041910B CN 116041910 B CN116041910 B CN 116041910B CN 202310165908 A CN202310165908 A CN 202310165908A CN 116041910 B CN116041910 B CN 116041910B
- Authority
- CN
- China
- Prior art keywords
- self
- healing
- epoxy resin
- composite material
- damping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000013016 damping Methods 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 56
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 19
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 33
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 230000008859 change Effects 0.000 description 31
- 239000000243 solution Substances 0.000 description 17
- 230000035876 healing Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000007717 exclusion Effects 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006299 self-healing polymer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 Glutaric anhydride Sebacic acid Chemical compound 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses a high-rigidity high-damping self-healing composite material based on epoxy resin and a preparation method thereof, belonging to the preparation technology of self-healing materials, wherein the preparation method comprises the following steps: uniformly dispersing carbon nanotubes in epoxy resin, and adding a catalyst and an anhydride curing agent to form an intermediate; and (3) curing the intermediate, wherein an anhydride curing agent reacts with the epoxy resin to generate ester bonds in the curing process, and the catalyst accelerates ester bond exchange to obtain the self-healing composite material. According to the invention, epoxy resin is used as a base material, an acid anhydride curing agent reacts with the epoxy resin to generate ester bonds, the ester bonds are subjected to reversible exchange reaction under the action of a catalyst, the self-healing function of the material is realized, the self-healing material is compounded with the carbon nano tube, and the rigidity of the material is enhanced by the carbon nano tube. At the same time, the reversible exchange reaction generates a large number of suspension chains at the molecular chain ends, causing viscous damping. The carbon nano tube contacts with the material at a microscopic scale to generate interface damping, so that the self-healing composite material has high rigidity and high damping performance.
Description
Technical Field
The invention belongs to the technical field of self-healing material preparation, and in particular relates to a high-rigidity high-damping self-healing composite material based on epoxy resin and a preparation method thereof.
Background
The traditional thermosetting resin realizes a three-dimensional crosslinked network by utilizing irreversible covalent bonds, and once the irreversible covalent bonds are broken, the irreversible covalent bonds cannot be rebuilt again, so that the problems of reprocessing and recycling of the composite material are further affected. The vitrimer self-healing composite material proposed in recent years is expected to become a new polymer material replacing the traditional thermosetting resin base material, thereby becoming a hot spot and an emerging field of the current technological front.
In self-healing polymeric materials, the bond energy of reversible covalent bonds tends to be weaker than the bond energy of irreversible covalent bonds, and reversible chemical bond cleavage tends to occur first when broken by a load. When the damaged parts are contacted with each other, reversible covalent bonds are formed again at the damaged interface of the polymer chain segment through local temperature excitation, the polymer chain segment is promoted to be sewn at the crack, and finally, the repair of statics and dynamic performance is realized. However, since the bond energy of the reversible covalent bond is weaker than that of the irreversible covalent bond, the self-healing material is made to have a slightly weaker stiffness and strength than conventional polymeric materials. The elastic modulus of the self-healing polymer material prepared at present is not high enough, and a certain gap exists between the self-healing polymer material and the common thermosetting resin-based composite material. And with the development of modern technology to the directions of multifunctional integration, light weight, comfort, intelligence and the like, the composite material is required to have high mechanical property and high damping property in a wide and dense excitation spectrum environment. For most structural materials, the combination of high rigidity and high damping is crucial, but the rigidity and the damping are two mutually exclusive properties, so how to make the composite material have the combination of high rigidity and high damping is one of academic research hot spots.
Therefore, the existing self-healing material has the technical problems of insufficient mechanical property of the material and mutual exclusion between the rigidity and damping properties.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a high-rigidity high-damping self-healing composite material based on epoxy resin and a preparation method thereof, thereby solving the technical problems of insufficient mechanical property, mutual exclusion between rigidity and damping performance of the existing self-healing material.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a high-rigidity high-damping self-healing composite material based on epoxy resin, comprising the steps of:
(1) Uniformly dispersing carbon nanotubes in epoxy resin, and then adding a catalyst and an anhydride curing agent to form an intermediate;
(2) And (3) curing the intermediate, wherein an anhydride curing agent reacts with the epoxy resin to generate an ester bond in the curing process, the catalyst accelerates the ester bond exchange process, and the self-healing composite material with the exchange bond of the ester bond and the carbon nano tube is obtained by curing.
Further, the anhydride curing agent is glutaric anhydride, and the glass transition temperature of the self-healing composite material is 64-66 ℃.
Further, the anhydride curing agent is a mixture of glutaric anhydride and sebacic acid, and the glass transition temperature of the self-healing composite material is 50-52 ℃.
Further, the molar ratio of glutaric anhydride and sebacic acid is (1-3): 1.
further, the step (2) includes:
preheating a die, and then injecting the intermediate subjected to the vacuumizing treatment into the die;
and sequentially carrying out vacuumizing treatment and heating solidification on the intermediate in the die to obtain the self-healing composite material.
Further, the intermediate is injected into the mold by:
the intermediate is drawn in from the bottom of the container in which it is placed by a syringe and injected into the mold.
Further, the preheating temperature of the die is 40-60 ℃, the preheating time is 20-40 min, the heating and curing process is 120-130 ℃, the heating is carried out for 1-3 h, the heating is 150-160 ℃, the heating is carried out for 1-3 h, the heating is carried out for 170-180 ℃, and the heating is carried out for 1-3 h.
Further, the step (1) includes:
mixing the multi-wall carbon nano tube and the epoxy resin to obtain a mixed solution, and stirring and ultrasonically vibrating the mixed solution to uniformly disperse the multi-wall carbon nano tube in the epoxy resin; then adding a catalyst and an anhydride curing agent, and uniformly mixing to form an intermediate.
Further, the molar ratio of the epoxy group to the curing agent in the epoxy resin is 2:1, and the molar ratio of the anhydride curing agent to the catalyst is 100: (9-11), the mass percentage of the carbon nano tube and the mass sum of the epoxy resin, the anhydride curing agent and the catalyst is 0.09-0.11%.
Further, the catalyst is zinc acetylacetonate, the epoxy resin is bisphenol A type epoxy resin, the purity of the multi-wall carbon nano tube is more than or equal to 98%, the outer diameter is 20-30nm, and the length is 0.5-2 mu m.
According to another aspect of the invention, there is provided an epoxy resin-based high-rigidity high-damping self-healing composite material, the self-healing composite material being prepared by a preparation method of the epoxy resin-based high-rigidity high-damping self-healing composite material, the self-healing composite material comprising a self-healing material with exchange bonds as ester bonds and carbon nanotubes, the carbon nanotubes being located in a cross-linked network of the self-healing material and being in contact with the self-healing material on a microscopic scale to generate an interface damping effect.
In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:
(1) The self-healing material prepared by the method takes epoxy resin as a base material, generates ester bonds through the reaction of an anhydride curing agent and the epoxy resin, and generates ester bonds through reversible exchange reaction under the catalysis of a catalyst, thereby obtaining the self-healing material with the self-healing function. Aiming at the problem of insufficient mechanical property of the self-healing material and solving the contradiction problem between two mutual exclusion properties of damping and rigidity in the self-healing material, the invention uses the characteristics of the biological boundary structural material to hope to realize the high-rigidity and high-damping performance of the material by taking into consideration the new structural damping effect of mutual complementation and interaction and mutual restriction of each phase characteristic structure of a plurality of spatial dimensions through the gradient structure of the multi-level characteristic substructure. Therefore, the method is that the carbon nano tube is uniformly dispersed in the epoxy resin, and then the curing treatment is carried out, so that the self-healing material and the carbon nano tube are compounded. On the one hand, the addition of the carbon nanotubes enhances the mechanical properties of the material, and on the other hand, the substrate causes viscous damping at the end of the molecular chain based on a large number of dangling chains generated by the reversible exchange reaction. On a molecular scale, the polymer of the self-healing material provides good damping. The addition of the carbon nano tube generates an interface damping effect when contacting with the self-healing material on a microscopic scale, so that the self-healing composite material has high rigidity and high damping performance.
(2) The preparation method not only solves the technical problems of insufficient mechanical property, mutual exclusion between rigidity and damping performance of the existing self-healing material, but also produces unexpected technical effects: on the premise of not reducing the performance of the self-healing composite material, the glass transition temperature of the self-healing composite material can be regulated and controlled by controlling the type of the anhydride curing agent. The glass transition temperature of the sebacic acid cured epoxy resin in the mixed curing agent is lower than that of the glutaric anhydride cured epoxy resin, so that the glass transition temperature of the self-healing composite material prepared by the mixed curing agent is reduced by 14-16 ℃ compared with that of the material prepared by the single curing agent, and the glass transition temperature of the material is regulated. Experimental data prove that the self-healing composite material prepared under the condition of using different anhydride curing agents has high rigidity and high damping performance.
(3) The air bubbles generated in the curing process of the epoxy resin can directly influence the performance of the cured material, so that the generation of the air bubbles is reduced as much as possible in the curing process of the material. Firstly, the mold is preheated, then the solution subjected to the vacuumizing treatment is transferred to the mold, and then the solution in the mold is vacuumized again, so that the generation of bubbles can be effectively reduced. Because bubbles easily exist on the surface of the solution, the intermediate is pumped from the bottom of the container for placing the intermediate by using the syringe, so that the generation of bubbles can be further reduced, and the mechanical property of the self-healing composite material is further improved.
(4) Nanofillers are ideal reinforcing phase materials for improving the structural function of composite materials because of their light weight and excellent mechanical properties. However, since poor compatibility of the carbon nanotubes with the epoxy resin affects the composite material properties, it is necessary to ensure that the carbon nanotubes are well dispersed in the epoxy resin. The compatibility problem of the carbon nano tube and the epoxy resin can be effectively improved by stirring the mixed solution and adding ultrasonic vibration, so that the carbon nano tube is more uniformly dispersed in the matrix. The multi-wall carbon nano tube is selected because the interaction force is also generated between the walls inside the multi-wall carbon nano tube, thereby being beneficial to improving the damping of the composite material.
Drawings
FIG. 1 is a preparation flow chart provided by an embodiment of the present invention;
FIG. 2 (a) is a graph of loss modulus versus temperature change provided in example 1 of the present invention;
FIG. 2 (b) is a graph of storage modulus versus temperature change provided in example 1 of the present invention;
FIG. 2 (c) is a graph of damping loss factor versus temperature change provided in example 1 of the present invention;
FIG. 3 (a) is a graph of loss modulus versus temperature change provided in example 2 of the present invention;
FIG. 3 (b) is a graph of storage modulus versus temperature change provided in example 2 of the present invention;
FIG. 3 (c) is a graph of damping loss factor versus temperature change provided in example 2 of the present invention;
FIG. 4 (a) is a graph of loss modulus versus temperature change provided in example 3 of the present invention;
FIG. 4 (b) is a graph of storage modulus versus temperature change provided in example 3 of the present invention;
FIG. 4 (c) is a graph of damping loss factor versus temperature change provided in example 3 of the present invention;
FIG. 5 (a) is a graph of loss modulus versus temperature change provided by comparative example 1 of the present invention;
FIG. 5 (b) is a graph of storage modulus versus temperature change provided by comparative example 1 of the present invention;
FIG. 5 (c) is a graph of damping loss factor versus temperature change provided by comparative example 1 of the present invention;
FIG. 6 (a) is a graph of loss modulus versus temperature change provided in example 4 of the present invention;
FIG. 6 (b) is a graph of storage modulus versus temperature change provided in example 4 of the present invention;
FIG. 6 (c) is a graph of damping loss factor versus temperature change provided in example 4 of the present invention;
FIG. 7 (a) is a drawing of tensile stress versus strain for sample No. 1 provided in the examples of the present invention;
FIG. 7 (b) is a drawing of tensile stress versus strain for sample No. 2 provided by the examples of this invention;
FIG. 7 (c) is a drawing of tensile stress versus strain for sample No. 3 provided by the examples of this invention;
FIG. 8 (a) is a plot of tensile stress versus strain for a material after healing for sample number 1 provided in an embodiment of the present invention;
FIG. 8 (b) is a plot of tensile stress versus strain for sample No. 2 provided by the examples of the present invention after healing;
fig. 8 (c) is a tensile stress-strain diagram of the material after healing of sample No. 3 provided in the example of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention is mainly designed to solve the problem of insufficient mechanical property of self-healing materials and the contradiction between two mutual exclusion properties of damping and rigidity in self-healing materials. In order to solve the contradiction between mutual exclusion performances such as rigidity and damping, the invention uses the characteristics of the biological world structural material to hope to realize the high rigidity and high damping performance of the material by taking into consideration the new structural damping effect that the characteristic structures of each phase of a plurality of spatial scales are mutually complemented and mutually restricted by each other through the gradient structure of the multi-layer characteristic substructure. By doping the nanofiller, the cross-linked network topology of the self-healing composite substrate can affect the interface characteristics driven by the nanofiller, thereby affecting the stiffness and damping properties of the self-healing composite. Therefore, the invention designs the composite characteristic structure of the self-healing base material on the nano, micro and meso scale by doping the carbon nano tube filler. On the molecular chain end scale, there are a large number of dangling chains based on self-healing reversible exchange, causing viscous damping. On a macromolecular scale, the macromolecular chains of the substrate itself provide good damping. The doped carbon nano tube contacts with the base material on a microscopic scale to generate an interface damping effect, so that the gradient structure of the multi-level characteristic substructure is realized. Compared with the prior art, the invention utilizes the carbon nano tube to enhance the mechanical property of the material, and simultaneously focuses on the interface damping effect generated by the contact of the nano material with the base material on the microscopic scale, and simultaneously, the self-healing material causes viscous damping based on a suspension chain generated by the reversible exchange reaction, so that the material can be ensured to have high rigidity and high damping performance. The loss modulus E (an index representing the comprehensive performance of the rigidity and the damping of the material) of the material prepared by the process of the design of the invention reaches 1242MPa, which exceeds 600MPa of the traditional material.
As shown in FIG. 1, the preparation method of the high-rigidity high-damping self-healing composite material based on the epoxy resin comprises the following steps:
(1) Uniformly dispersing carbon nanotubes in epoxy resin, and then adding a catalyst and an anhydride curing agent to form an intermediate;
(2) And (3) curing the intermediate, wherein an anhydride curing agent reacts with the epoxy resin to generate an ester bond in the curing process, the catalyst accelerates the ester bond exchange process, and the self-healing composite material with the exchange bond of the ester bond and the carbon nano tube is obtained by curing.
Specifically, step (1) includes:
and A1, adding the multiwall carbon nanotubes into a beaker, pouring epoxy resin into the beaker for mixing, and stirring the mixed solution under a mechanical stirrer with the rotating speed of 1500-2000 r/min while carrying out ultrasonic vibration for 3 hours to form an intermediate 1.
And A2, adding zinc acetylacetonate into the intermediate 1, heating to 150 ℃, and stirring for 0.5h at the rotating speed of 1000r/min to obtain the intermediate 2.
And step A3, cooling the intermediate 2 to 50 ℃, adding a glutaric anhydride and sebacic acid mixed curing agent, and stirring for 1h at the temperature of 50 ℃ and the rotating speed of 1500-2000 r/min to obtain an intermediate 3.
The step (2) comprises:
and A4, placing the mixed solution into a vacuum incubator for vacuumizing treatment. A layer of release agent is coated on the surface of the mould, and then the mould is placed in a vacuum incubator and heated for 30min at 50 ℃.
And step A5, sucking the prepared solution (sucking the solution at the bottom of the beaker as much as possible, wherein bubbles are easy to exist on the surface of the solution) by using a syringe, and injecting the solution into a die.
Step A6: putting the die into a vacuum incubator, opening a vacuumizing switch until the air pressure is reduced to-93 KPa, keeping the air pressure for 10min, opening a piston for deflation, and vacuumizing for 2-3 times.
Step A7: the temperature in the vacuum incubator is regulated, and the curing process is as follows: 130 ℃/2 h-160 ℃/2 h-180 ℃/2h.
Example 1
The raw materials used comprise epoxy resin, a mixed curing agent and a catalyst, wherein the dosage ratio of the epoxy group, the mixed curing agent and the catalyst in the epoxy resin is 1mol:0.5mol:0.05mol of glutaric anhydride in the mixed curing agent: the dosage ratio of sebacic acid is 0.375mol:0.125mol, 0.1wt.% multiwall carbon nanotubes.
The preparation method of the high-rigidity high-damping self-healing composite material based on the epoxy resin comprises the following steps:
and A1, adding the multi-wall carbon nano tube (0.1 wt.%,0.274 g) into a beaker, pouring the epoxy resin (200 g) into the beaker for mixing, and stirring the mixed solution under a mechanical stirrer with the rotating speed of 1500-2000 r/min while carrying out ultrasonic vibration for 3 hours to form the intermediate 1.
Step A2, zinc acetylacetonate (0.05 mol,13.588 g) was added to intermediate 1, the temperature was raised to 150℃and stirred at 1000r/min for 0.5h to give intermediate 2.
Step A3, cooling the intermediate 2 to 50 ℃, adding glutaric anhydride (0.375 mol,45 g) and sebacic acid (0.125 mol,25.75 g) mixed curing agent, and stirring for 1h at 50 ℃ and the rotating speed of 1500-2000 r/min to obtain the intermediate 3.
And A4, placing the mixed solution into a vacuum incubator for vacuumizing treatment. A layer of release agent is coated on the surface of the mould, and then the mould is placed in a vacuum incubator and heated for 30min at 50 ℃.
And step A5, sucking the prepared solution (sucking the solution at the bottom of the beaker as much as possible, wherein bubbles are easy to exist on the surface of the solution) by using a syringe, and injecting the solution into a die.
Step A6: putting the die into a vacuum incubator, opening a vacuumizing switch until the air pressure is reduced to-93 KPa, keeping the air pressure for 10min, opening a piston for deflation, and vacuumizing for 2-3 times.
Step A7: the temperature in the vacuum incubator is regulated, and the curing process is as follows: 130 ℃/2 h-160 ℃/2 h-180 ℃/2h.
Example 2 the procedure was as in example 1, varying the molar ratio of the mixed curatives, glutaric anhydride (0.333 mol,40 g) and sebacic acid (0.167 mol,34.3 g).
Example 3 the procedure of example 1 was followed, varying the molar ratio of the mixed curative, glutaric anhydride (0.25 mol,30 g) and sebacic acid (0.25 mol,51.5 g).
Example 4 the procedure was as in example 1 except that the curing agent used was glutaric anhydride alone (0.5 mol,60 g).
Comparative example 1
Step A1 epoxy resin (200 g) was poured into a beaker.
Step A2, adding zinc acetylacetonate (0.05 mol,13.588 g) into a beaker, heating to 150 ℃, and stirring at a rotating speed of 1000r/min for 0.5h to obtain an intermediate 2.
Step A3, cooling the intermediate 2 to 50 ℃, adding glutaric anhydride (0.375 mol,45 g) and sebacic acid (0.125 mol,25.75 g) mixed curing agent, and stirring for 1h at 50 ℃ and the rotating speed of 1500-2000 r/min to obtain the intermediate 3.
And A4, placing the mixed solution into a vacuum incubator for vacuumizing treatment. A layer of release agent is coated on the surface of the mould, and then the mould is placed in a vacuum incubator and heated for 30min at 50 ℃.
And step A5, sucking the prepared solution (sucking the solution at the bottom of the beaker as much as possible, wherein bubbles are easy to exist on the surface of the solution) by using a syringe, and injecting the solution into a die.
Step A6: putting the die into a vacuum incubator, opening a vacuumizing switch until the air pressure is reduced to-93 KPa, keeping the air pressure for 10min, opening a piston for deflation, and vacuumizing for 2-3 times.
Step A7: the temperature in the vacuum incubator is regulated, and the curing process is as follows: 130 ℃/2 h-160 ℃/2 h-180 ℃/2h.
Example 5 the same procedure as in example 1 was followed except that the molar ratio of epoxy groups to curing agent in the epoxy resin in the starting material was 2:1 and the molar ratio of anhydride-based curing agent to catalyst was 100:9, the mass percentage of the carbon nano tube and the mass sum of the epoxy resin, the anhydride curing agent and the catalyst is 0.09 percent.
Example 6 the same procedure as in example 1 was followed except that the molar ratio of epoxy groups to curing agent in the epoxy resin in the starting material was 2:1 and the molar ratio of anhydride-based curing agent to catalyst was 100:11, the mass percentage of the carbon nano tube and the mass sum of the epoxy resin, the anhydride curing agent and the catalyst is 0.11 percent.
Example 7 example 1 was prepared as described above, except that the preheating and curing conditions were varied. The preheating temperature of the die is 40 ℃, the preheating time is 40min, the heating and curing process is 120 ℃, the heating is carried out for 3h, the heating is carried out for 150 ℃, the heating is carried out for 3h, the heating is carried out for 170 ℃, and the heating is carried out for 3h.
Example 8 example 1 was prepared as described above, except that the preheating and curing conditions were varied. The preheating temperature of the die is 60 ℃, the preheating time is 20min, the heating and curing process is 128 ℃, the heating is carried out for 1h and 158 ℃, the heating is carried out for 1h and 178 ℃, and the heating is carried out for 1h.
The composition ratios of examples 1 to 4 and comparative example 1 are shown in Table 1.
TABLE 1
Epoxy resin | Carbon nanotubes | Catalyst | Glutaric anhydride | Sebacic acid | |
Example 1 | 200 | 0.274 | 13.588 | 45 | 25.75 |
Example 2 | 200 | 0.274 | 13.588 | 40 | 34.3 |
Example 3 | 200 | 0.274 | 13.588 | 30 | 51.5 |
Comparative example 1 | 200 | - | 13.588 | 45 | 25.75 |
Example 4 | 200 | 0.274 | 13.588 | 60 | - |
The damping loss factor, the storage modulus and the loss modulus are tested by adopting the GB/T40396-2021 standard. The temperature corresponding to the highest peak of the damping loss factor is adopted as the glass transition temperature T g . The test results are shown in Table 2.
TABLE 2
FIG. 2 (a) is a graph of loss modulus versus temperature change provided in example 1 of the present invention, and it can be seen that when the curing agent is glutaric anhydride and sebacic acid in a molar ratio of 3:1, the maximum loss modulus of the prepared self-healing composite material is 1242MPa; FIG. 2 (b) is a graph of storage modulus versus temperature change provided in example 1 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 3:1, the maximum storage modulus of the prepared self-healing composite material is 4548MPa; FIG. 2 (c) is a graph of damping loss factor versus temperature change provided in example 1 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 3:1, the maximum damping loss factor of the prepared self-healing composite material is 0.77.
FIG. 3 (a) is a graph of loss modulus versus temperature change provided in example 2 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 2:1, the maximum loss modulus of the prepared self-healing composite material is 650MPa; FIG. 3 (b) is a graph of storage modulus versus temperature change provided in example 2 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 2:1, the maximum storage modulus of the prepared self-healing composite material is 4134MPa; FIG. 3 (c) is a graph of damping loss factor versus temperature change provided in example 2 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 2:1, the maximum damping loss factor of the prepared self-healing composite material is 1.12.
FIG. 4 (a) is a graph of loss modulus versus temperature change provided in example 3 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 1:1, the maximum loss modulus of the prepared self-healing composite material is 556MPa; FIG. 4 (b) is a graph of storage modulus versus temperature change provided in example 3 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 1:1, the maximum storage modulus of the prepared self-healing composite material is 3921MPa; FIG. 4 (c) is a graph of damping loss factor versus temperature change provided in example 3 of the present invention; it can be seen that when the curing agent is glutaric anhydride and sebacic acid with the molar ratio of 1:1, the maximum damping loss factor of the prepared self-healing composite material is 1.09.
FIG. 5 (a) is a graph of loss modulus versus temperature change provided by comparative example 1 of the present invention, FIG. 5 (b) is a graph of storage modulus versus temperature change provided by comparative example 1 of the present invention, and FIG. 5 (c) is a graph of damping loss factor versus temperature change provided by comparative example 1 of the present invention; it can be seen that the maximum loss modulus, the maximum damping loss factor and the maximum storage modulus of the prepared product are smaller than those of examples 1-3 without adding carbon nanotubes. The comparison of the embodiment and the comparative example 1 proves that the mechanical property of the material is greatly improved after the carbon nano tube and the self-healing material are compounded, and the material has high rigidity and high damping property.
Test data show that the maximum damping loss factor of the carbon nano tube/epoxy resin self-healing composite material prepared in the embodiment 1-3 is 0.77-1.12, the maximum storage modulus is 3921-4548MPa, and the maximum loss modulus is 556-1242MPa. The maximum loss modulus of examples 1-2 exceeds the limit value of 600MPa of the loss modulus of the traditional material, which shows that the invention has good rigidity and damping performance. The maximum storage modulus of the material reaches 4.5GPa, which shows that the self-healing material has good mechanical property.
FIG. 6 (a) is a graph of loss modulus versus temperature change provided in example 4 of the present invention; FIG. 6 (b) is a graph of storage modulus versus temperature change provided in example 4 of the present invention; FIG. 6 (c) is a graph of damping loss factor versus temperature change provided in example 4 of the present invention; it can be seen that the maximum storage modulus of the material prepared from the glutaric anhydride serving as a single curing agent reaches 4934MPa, and the maximum loss modulus reaches 682MPa. By observing examples 1-4, it can be found that the glass transition temperature (Tg) of the self-healing material prepared by mixing the curing agent is reduced by 14-16 ℃ compared with the Tg of the material prepared by mixing the curing agent alone, which shows that the invention can regulate and control the glass transition temperature of the material by regulating and controlling the type of the curing agent on the premise of ensuring the performance of the material.
The maximum damping loss factor, the maximum storage modulus and the maximum loss modulus of the self-healing composite materials prepared in the examples 5 and 6 are close to those of the example 3, and in combination with the examples 1, 5 and 6, it can be stated that the molar ratio of epoxy groups and curing agents in epoxy resin is 2:1, and the molar ratio of anhydride curing agents to catalysts is 100: (9-11), the mass percentage of the carbon nano tube and the sum of the mass percentages of the epoxy resin, the anhydride curing agent and the catalyst is 0.09% -0.11%, and the composite material with high rigidity and high damping performance can be prepared.
The maximum damping loss factor, the maximum storage modulus and the maximum loss modulus of the self-healing composite materials prepared in the examples 7 and 8 are close to those of the example 2, and the examples 1, 7 and 8 are combined together, so that the composite materials with high rigidity and high damping performance can be prepared by preheating and curing conditions in the range of 'the preheating temperature of the mould is 40-60 ℃, the preheating time is 20-40 min, the heating curing process is 120-130 ℃, the heating time is 1-3 h, the heating time is 150-160 ℃, the heating time is 1-3 h, the heating time is 170-180 ℃ and the heating time is 1-3 h'.
Examples 1-8 are combined to show that the carbon nano tube is well dispersed in the epoxy resin in the preparation process of the invention, and a new interface damping effect can be developed while the self-healing structure function is ensured, so that the damping performance is further improved on the basis of the viscoelastic damping characteristic of the self-healing base material, the contradiction between the two mutual exclusion performances of the material rigidity and the damping is improved, the problem of insufficient rigidity of the self-healing material is solved, and the self-healing composite material with high rigidity and high damping is prepared.
In order to characterize the self-healing performance of the material, a uniaxial stretching experiment is carried out on a sample, the elastic constant of the sample is measured, the stretched and broken sample is cast and cured again, the uniaxial stretching experiment is carried out on the healed sample, and whether the fracture surface of the sample is consistent before and after healing and the change condition of the elastic constant before and after healing are observed to characterize the self-healing performance of the material. The elastic constant of the material was determined using GB/T2567-2008. The samples were sample No. 1, sample No. 2 and sample No. 3 prepared by example 4. The properties of the materials prepared under the same preparation conditions are slightly different, but the loss modulus E of the three samples exceeds 600MPa of the traditional materials, which indicates that the rigidity and damping performance of the three samples are good.
Fig. 7 (a) is a drawing of tensile stress-strain of the material before healing of sample No. 1 provided by the embodiment of the present invention, fig. 7 (b) is a drawing of tensile stress-strain of the material before healing of sample No. 2 provided by the embodiment of the present invention, fig. 7 (c) is a drawing of tensile stress-strain of the material before healing of sample No. 3 provided by the embodiment of the present invention, fig. 8 (a) is a drawing of tensile stress-strain of the material after healing of sample No. 1 provided by the embodiment of the present invention, fig. 8 (b) is a drawing of tensile stress-strain of the material after healing of sample No. 2 provided by the embodiment of the present invention, and fig. 8 (c) is a drawing of tensile stress-strain of the material after healing of sample No. 3 provided by the embodiment of the present invention. By comparing the tensile fracture surfaces before and after the sample is healed, the tensile fracture surfaces before and after the sample is healed are found to be inconsistent, which indicates that the sample is healed in the curing process, otherwise the tensile fracture surfaces before and after the tensile fracture surfaces are consistent. The self-healing rates of the sample No. 1, the sample No. 2 and the sample No. 3 are calculated to be 55.30%,67.37% and 66.56% respectively for the variation of the elastic constants before and after the sample healing, which shows that the material has good self-healing performance. The self-healing material vitrimer takes epoxy resin as a base material, is cured by a curing agent, and generates ester bond reversible exchange reaction under the catalysis of a catalyst so as to ensure the self-healing function of the self-healing material.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The preparation method of the high-rigidity high-damping self-healing composite material based on the epoxy resin is characterized by comprising the following steps of:
(1) Mixing the multiwall carbon nanotube and epoxy resin to obtain a mixed solution, stirring the mixed solution under a mechanical stirrer at a rotating speed of 1500-2000 r/min while ultrasonically vibrating for 3 hours to form an intermediate 1, adding zinc acetylacetonate serving as a catalyst into the intermediate 1, heating to 150 ℃, stirring at a rotating speed of 1000r/min for 0.5 hours to obtain an intermediate 2, cooling the intermediate 2 to 50 ℃, adding an anhydride curing agent, stirring at a rotating speed of 1500-2000 r/min for 1 hour, and uniformly mixing to form an intermediate 3;
(2) Firstly preheating a mould, then sucking the intermediate 3 subjected to vacuumizing treatment from the bottom of a container for placing the intermediate by using a syringe, injecting the intermediate 3 into the mould, sequentially carrying out vacuumizing treatment and heating curing on the intermediate 3 in the mould, enabling an anhydride curing agent to react with epoxy resin to generate ester bonds in the curing process, enabling a catalyst to accelerate the ester bond exchange process, and curing to obtain a self-healing composite material with the exchange bonds being the ester bonds and a self-healing composite material compounded by the carbon nano tubes;
the anhydride curing agent is a mixture of glutaric anhydride and sebacic acid, and the glass transition temperature of the self-healing composite material is 50-52 ℃;
the purity of the multi-wall carbon nano tube is more than or equal to 98%, the outer diameter is 20-30nm, and the length is 0.5-2 mu m;
the molar ratio of the glutaric anhydride to the sebacic acid is (1-3): 1;
the preheating temperature of the die is 40-60 ℃, the preheating time is 20-40 min, the heating and curing process is 120-130 ℃, the heating is carried out for 1-3 h, the heating is 150-160 ℃, the heating is carried out for 1-3 h, the heating is carried out for 170-180 ℃, and the heating is carried out for 1-3 h.
2. The preparation method of the high-rigidity high-damping self-healing composite material based on the epoxy resin, which is disclosed in claim 1, is characterized in that the molar ratio of epoxy groups to curing agents in the epoxy resin is 2:1, the molar ratio of anhydride curing agents to catalysts is 100 (9-11), and the percentage of the mass of the carbon nano tube to the sum of the mass of the epoxy resin, the anhydride curing agents and the catalysts is 0.09% -0.11%.
3. The epoxy resin-based high-rigidity high-damping self-healing composite material is characterized in that the self-healing composite material is prepared by the preparation method of the epoxy resin-based high-rigidity high-damping self-healing composite material in claim 1 or 2, and the self-healing composite material comprises self-healing materials with exchange bonds as ester bonds and carbon nanotubes, wherein the carbon nanotubes are positioned in a cross-linked network of the self-healing materials, and contact with the self-healing materials on a microscopic scale to generate an interface damping effect.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310165908.7A CN116041910B (en) | 2023-02-24 | 2023-02-24 | High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310165908.7A CN116041910B (en) | 2023-02-24 | 2023-02-24 | High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116041910A CN116041910A (en) | 2023-05-02 |
CN116041910B true CN116041910B (en) | 2024-02-02 |
Family
ID=86113486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310165908.7A Active CN116041910B (en) | 2023-02-24 | 2023-02-24 | High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116041910B (en) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1425642A (en) * | 2002-12-20 | 2003-06-25 | 中国科学院广州化学研究所 | Method of catalyzing esterification of carboxylic acid and expoxy compound |
CN101775194A (en) * | 2010-02-10 | 2010-07-14 | 上海理工大学 | Carbon nano tube/epoxide resin composite material and preparation method thereof |
WO2012066244A1 (en) * | 2010-11-17 | 2012-05-24 | Arkema France | Masterbatch of carbon nanotubes and curing agent for thermosetting resins |
CN103314030A (en) * | 2011-01-24 | 2013-09-18 | 法国国家科学研究中心 | Hot-formable and recyclable epoxy anhydride thermosetting resins and thermosetting composites |
CN110041514A (en) * | 2019-05-13 | 2019-07-23 | 无锡风鹏新材料科技有限公司 | A kind of lower glass transition temperatures, dystectic tough polyesters plastics and preparation method thereof |
CN111763404A (en) * | 2020-07-17 | 2020-10-13 | 中国空间技术研究院 | Conductive glass polymer material and preparation method thereof |
CN112852109A (en) * | 2021-01-14 | 2021-05-28 | 成都谦智明远科技有限公司 | Preparation method of high-temperature self-repairing hot-mix epoxy asphalt material |
CN112961463A (en) * | 2021-02-07 | 2021-06-15 | 四川大学 | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof |
CN113150502A (en) * | 2021-04-06 | 2021-07-23 | 中国空间技术研究院 | Electrically-driven glass polymer material and preparation method thereof |
WO2022095286A1 (en) * | 2020-11-03 | 2022-05-12 | 南京大学 | Epoxy resin-based polymer material, preparation method therefor and use thereof |
-
2023
- 2023-02-24 CN CN202310165908.7A patent/CN116041910B/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1425642A (en) * | 2002-12-20 | 2003-06-25 | 中国科学院广州化学研究所 | Method of catalyzing esterification of carboxylic acid and expoxy compound |
CN101775194A (en) * | 2010-02-10 | 2010-07-14 | 上海理工大学 | Carbon nano tube/epoxide resin composite material and preparation method thereof |
WO2012066244A1 (en) * | 2010-11-17 | 2012-05-24 | Arkema France | Masterbatch of carbon nanotubes and curing agent for thermosetting resins |
CN103314030A (en) * | 2011-01-24 | 2013-09-18 | 法国国家科学研究中心 | Hot-formable and recyclable epoxy anhydride thermosetting resins and thermosetting composites |
CN110041514A (en) * | 2019-05-13 | 2019-07-23 | 无锡风鹏新材料科技有限公司 | A kind of lower glass transition temperatures, dystectic tough polyesters plastics and preparation method thereof |
CN111763404A (en) * | 2020-07-17 | 2020-10-13 | 中国空间技术研究院 | Conductive glass polymer material and preparation method thereof |
WO2022095286A1 (en) * | 2020-11-03 | 2022-05-12 | 南京大学 | Epoxy resin-based polymer material, preparation method therefor and use thereof |
CN112852109A (en) * | 2021-01-14 | 2021-05-28 | 成都谦智明远科技有限公司 | Preparation method of high-temperature self-repairing hot-mix epoxy asphalt material |
CN112961463A (en) * | 2021-02-07 | 2021-06-15 | 四川大学 | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof |
CN113150502A (en) * | 2021-04-06 | 2021-07-23 | 中国空间技术研究院 | Electrically-driven glass polymer material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN116041910A (en) | 2023-05-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5403184B1 (en) | Fiber reinforced composite material | |
JP5454138B2 (en) | Epoxy resin composition, fiber-reinforced composite material, and method for producing the same | |
CN106543647B (en) | A kind of high tenacity, low temperature resistant resin matrix and preparation method thereof | |
CN103965582B (en) | For carbon nano double cured resin matrix and the matrix material of pultrusion molding process | |
CN109265922B (en) | High-toughness autocatalytic epoxy resin and preparation method thereof | |
TW201841970A (en) | Epoxy resin composition for fiber-reinforced composite materials, fiber-reinforced composite material and molded body | |
CN103965590B (en) | Epoxy resin composite material of a kind of coordination plasticizing and preparation method thereof | |
CN110437587B (en) | Carbon fiber composite resin for wind power blade and preparation method thereof | |
CN101343399A (en) | Immingled filling material filled polyurethane modified epoxy resin embedding material and preparation method | |
JPH09137043A (en) | Epoxy resin composition | |
CN102850545A (en) | High-toughness high-heat-resistant poly-benzoxazine/ bismaleimide blending resin and preparation method thereof | |
CN106753218B (en) | A kind of low dielectric high tenacity cyanate ester adhesive and preparation method thereof | |
CN111393800A (en) | Epoxy resin suitable for pultrusion process and carbon fiber composite material thereof | |
CN113943473A (en) | High-toughness epoxy resin composition and preparation process thereof | |
CN107011657A (en) | A kind of high-ductility bimaleimide resin and its preparation method and application | |
WO2024037194A1 (en) | Epoxy resin composition having two-phase sea-island structure, composite material, and preparation methods therefor | |
CN112194900A (en) | Silicon rubber mold for integral molding of composite skirt and preparation method thereof | |
CN113201207A (en) | Preparation method of high-toughness and high-strength carbon nanotube/epoxy resin composite material | |
CN103304960B (en) | A kind of preparation method of two-arch tunnel POSS-epoxy modified resin | |
CN116041910B (en) | High-rigidity high-damping self-healing composite material based on epoxy resin and preparation method thereof | |
CN1749452A (en) | Jelly spinning polyethylene/epoxy resin composite fiber and its preparing method | |
CN112961468B (en) | Modified epoxy resin composite material and preparation method thereof | |
CN104448711B (en) | Epoxy resin/carbon fiber/halloysite nanotube composite material and preparation method thereof | |
CN106117980A (en) | A kind of self reinforcing resin system and preparation method thereof in situ | |
CN109385045B (en) | Medium-temperature cured high-toughness epoxy resin and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |