CN114015202A - Temperature response shape memory epoxy resin, composite material and preparation method - Google Patents
Temperature response shape memory epoxy resin, composite material and preparation method Download PDFInfo
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- CN114015202A CN114015202A CN202111271986.2A CN202111271986A CN114015202A CN 114015202 A CN114015202 A CN 114015202A CN 202111271986 A CN202111271986 A CN 202111271986A CN 114015202 A CN114015202 A CN 114015202A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/145—Compounds containing one epoxy group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/12—Shape memory
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Abstract
The invention provides a temperature response shape memory epoxy resin, a composite material and a preparation method thereof, wherein the composite material comprises the following components: 40-90 parts of hydroxyethylated bisphenol A epoxy resin and/or hydroxyethylated bisphenol fluorene epoxy resin and 10-60 parts of fiber reinforcement. The invention synthesizes a novel epoxy resin system containing a rigid aromatic ring unit and a flexible ethoxy unit by design, and simultaneously introduces a hard segment group and a soft segment group into an epoxy molecule, wherein the hard segment group is responsible for mechanical property, and the soft segment group is responsible for shape memory property; the cross-linking density and molecular chain flexibility of the epoxy resin network are regulated and controlled by changing the proportion of the hard segment to the soft segment, so that the regulation and control of the transition temperature range of 80-180 ℃ are realized; the fiber reinforcement with different contents is compounded with the epoxy resin, so that the shape memory performance and the mechanical property of the composite material are cooperatively optimized.
Description
Technical Field
The invention belongs to the technical field of shape memory composite materials, and particularly relates to a temperature response shape memory epoxy resin, a composite material and a preparation method.
Background
With the continuous deep utilization of space resources by human beings, the demands of spacecrafts on large space structures such as space science astronomical benches, antennas, solar cell arrays and the like of the large structures are more urgent recently and in the future. In order to save carrying space and energy consumption, a light expandable structure is produced, and the light expandable structure is in a folded state when being launched and is expanded into a working state after entering a preset track. The shape memory epoxy resin composite material has active deformation capacity under certain stimulation, and provides possibility for effectively solving the problem of unstable performance of the traditional mechanical drive.
The shape memory epoxy resins for space that have been reported at present abroad mainly include TP series epoxy resins developed by ILC and TEMBO series epoxy resins developed by CTD. The epoxy resins developed by ILC have relatively weak shape recovery stresses and are not generally formed into shape memory members alone. CTD compounds the thermosetting shape Memory epoxy resin with reinforcement to prepare the elastic Memory composite material EMC (elastic Memory composite). The reinforcing material comprises conventional reinforcing materials such as carbon fiber, glass fiber, Kevlar fiber and the like, and nano reinforcing materials. The EMC material not only retains the excellent mechanical deformation, storage strain and shape recovery performance of the TEMBO epoxy resin, but also has the mechanical properties of a reinforced high-strength high-modulus body and excellent space use performance. EMC materials have been made to date as components of various deployable structures, including lightweight, high stiffness, low stored strain energy, stored-tube-like extendable members, shock-free deployable hinge structures, stringer knuckles, structural beams, and the like.
In contrast, the research in the field of shape memory composite materials in China is relatively late, most of the materials are in the laboratory range, and the research stage of principle prototypes is adopted. The lack of excellent shape memory epoxy resin systems, the improvement of mechanical strength and the increase of deformability tend to "trade off". The introduction of fiber reinforcement in the resin system can improve its mechanical properties, but the effective strain of the fiber reinforcement phase is small (typically less than 2%) and does not have shape memory properties. Therefore, the content of the fiber reinforcement greatly affects the shape memory property and the mechanical property of the composite material, and the more the content of the fiber, the higher the mechanical property of the composite material, but the less the resin having the shape memory effect, the lower the shape fixation rate and the shape recovery rate of the composite material. In summary, for the shape memory epoxy resin composite material, the increase of the mechanical strength is usually accompanied with the reduction of the deformability, and the carbon fiber and the resin have an optimal functional matching, so that the composite material has the best comprehensive performance.
Disclosure of Invention
Aiming at the problem that the shape memory performance and the mechanical performance function matching performance of the current shape memory epoxy resin matrix composite material are poor, the inventor carries out intense research, provides a temperature response shape memory epoxy resin, a composite material and a preparation method, designs and synthesizes a novel epoxy resin containing a rigid aromatic ring unit and a flexible ethoxy unit, simultaneously introduces a 'hard segment' group and a 'soft segment' group into an epoxy molecule, the 'hard segment' is responsible for the mechanical performance, and the 'soft segment' is responsible for the shape memory performance; the cross-linking density and molecular chain flexibility of the epoxy resin network are regulated and controlled by changing the proportion of the hard segment to the soft segment, so that the regulation and control of the transition temperature range of 80-180 ℃ are realized; the invention is completed by adopting the composite of the fiber reinforcement with proper content and the epoxy resin to realize the cooperative optimization of the shape memory performance and the mechanical property of the composite material.
The technical scheme provided by the invention is as follows:
in a first aspect, a shape memory epoxy resin is a mixture of hydroxyethylated bisphenol a type epoxy resin and hydroxyethylated bisphenol fluorene type epoxy resin in any proportion;
the molecular structure of the hydroxyethylated bisphenol A epoxy resin contains 2 to 6 hydroxyethyl groups;
the hydroxyethylated bisphenol fluorene type epoxy resin takes bisphenol fluorene as a hard segment group and takes two hydroxyethyl groups as a soft segment group.
In a second aspect, a method for preparing a shape memory epoxy resin comprises the steps of:
step (1): mixing hydroxyethylated bisphenol A epoxy resin and hydroxyethylated bisphenol fluorene epoxy resin in certain proportion and heating to clear;
step (2): adding curing agents with equal metering ratio into the mixed liquid in the step (1), and uniformly stirring until the curing agents are completely dissolved;
and (3): degassing the mixture of step (2) in vacuum, and then pouring into a preheated mold;
and (4): and finishing the temperature programming curing process in an oven, a self-heating device or an autoclave mode to prepare the shape memory epoxy resin.
In a third aspect, the shape memory epoxy resin-based composite material comprises the following components in parts by mass:
40-90 parts of an epoxy resin matrix;
10-60 parts of a fiber reinforcement;
6.63-16.0 parts of a curing agent;
wherein the epoxy resin matrix is selected from at least one of hydroxyethylated bisphenol A epoxy resin or hydroxyethylated bisphenol fluorene epoxy resin, and the molecular structure of the hydroxyethylated bisphenol A epoxy resin contains 2-6 hydroxyethyl units; the hydroxyethylated bisphenol fluorene epoxy resin takes bisphenol fluorene as a hard segment group and two hydroxyethyl groups as a soft segment group; the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (100-60): (0-40).
In a fourth aspect, a method for preparing a shape memory epoxy resin-based composite material comprises the following steps:
step (1): uniformly mixing the selected epoxy resin matrix and the curing agent in proportion;
step (2): laying fiber reinforcement bodies in a mould according to the determined laying angle and the determined sequence;
and (3): injecting the preheated epoxy resin system in the step 1 from the glue injection port at a set temperature and pressure;
and (4): and finishing the temperature programming curing process in a baking oven, a self-heating device or an autoclave manner to prepare the shape memory epoxy resin matrix composite material.
According to the temperature response shape memory epoxy resin, the composite material and the preparation method provided by the invention, the following beneficial effects are achieved:
(1) the invention provides a temperature response shape memory epoxy resin, a composite material and a preparation method thereof, provides a novel epoxy resin matrix containing a rigid aromatic ring unit and a flexible ethoxy unit, wherein a hard section group and a soft section group are simultaneously introduced into an epoxy molecule, the hard section group is responsible for mechanical property, the soft section group is responsible for shape memory property, and a fiber reinforcement is matched to realize the cooperative optimization of the shape memory property and the mechanical property of the composite material;
(2) according to the temperature response shape memory epoxy resin, the composite material and the preparation method, the cross-linking density and the molecular chain flexibility of an epoxy resin network are regulated and controlled by changing the proportion of the hard segment to the soft segment, so that the regulation and control of the transition temperature range of 80-180 ℃ are realized;
(3) according to the temperature response shape memory epoxy resin, the composite material and the preparation method, the composite material is prepared by adopting a low-viscosity liquid molding process, the molding process is simple, the operation is convenient, no solvent is used, the environment is friendly, the product stability is good, the production efficiency is high, and the batch production is easy to realize;
(4) the invention provides a temperature response shape memory epoxy resin, a composite material and a preparation method thereof, and the prepared shape memory epoxy resin and the composite material thereof have excellent shape memory performance and mechanical property at the same time: the tensile strength of the epoxy resin at room temperature is 67.3MPa, the tensile modulus is 2.70GPa, and the shape fixing rate and the shape recovery rate are both more than 99 percent; the composite material has the tensile strength of 94.8MPa, the tensile modulus of 8.41GPa, the shape fixing rate of more than 96.1 percent and the shape recovery rate of more than 92.5 percent.
Drawings
FIG. 1 is a flow chart of the preparation of the shape memory epoxy resin based composite material of the present invention.
FIG. 2 shows the structural formula of the hydroxyethylated bisphenol fluorene epoxy resin of example 1 of the present invention.
FIG. 3 is an infrared spectrum of a hydroxyethylated bisphenol fluorene type epoxy resin in example 1 of the present invention.
FIG. 4 is a graph showing the shape recovery rate of the epoxy resin according to example 1 of the present invention at different recovery temperatures as a function of recovery time.
FIG. 5 shows the results of Dynamic Mechanical Analysis (DMA) tests of the shape-memory epoxy resin-based composite material in example 5 of the present invention.
FIG. 6 is a chart showing the shape recovery process of the shape memory epoxy resin based composite material of example 5 of the present invention, a) in an initial state, b) in an initial U-shape, c) in an oil bath for 5s, d)7s, e)9s, f)12s, g)15s, h)60s, i)20 min.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to a first aspect of the present invention, there is provided a shape memory epoxy resin which is a mixture of a hydroxyethylated bisphenol a type epoxy resin and a hydroxyethylated bisphenol fluorene type epoxy resin in an arbitrary ratio.
In a preferred embodiment, the hydroxyethylated bisphenol A epoxy resin contains 2 to 6 hydroxyethyl groups in its molecular structure.
In a preferred embodiment, the hydroxyethylated bisphenol fluorene type epoxy resin has bisphenol fluorene as the "hard segment" group and two hydroxyethyl groups as the "soft segment" groups. The hydroxyethylated bisphenol fluorene epoxy resin is prepared by the following method:
step (1): uniformly mixing 1 equivalent of fluorenyl bisphenol A polyether alcohol and 9-11 equivalents of propylene oxide in a solvent, and slowly heating to 40-60 ℃;
step (2): adding the mixed liquid obtained in the step (1) into 2-4 equivalents of sodium hydroxide in multiple equal parts, wherein the adding time interval of each part is 0.5-1 hour;
and (3): and (3) stirring the mixture in the step (2) at 40-60 ℃ for at least 1 h.
According to a second aspect of the present invention, there is provided a method for preparing a temperature-responsive shape-memory epoxy resin, comprising the steps of:
step (1): mixing hydroxyethylated bisphenol A epoxy resin and hydroxyethylated bisphenol fluorene epoxy resin in certain proportion and heating to clear;
step (2): adding curing agents with equal metering ratio into the mixed liquid in the step (1), and uniformly stirring until the curing agents are completely dissolved;
and (3): degassing the mixture of step (2) in vacuum, and then pouring into a preheated mold;
and (4): and finishing the temperature programming curing process in a baking oven, a self-heating device or an autoclave and the like to prepare the shape memory epoxy resin.
In this embodiment, in step (1), the hydroxyethylated bisphenol A type epoxy resin and the hydroxyethylated bisphenol fluorene type epoxy resin may be mixed in an arbitrary ratio.
In a preferred embodiment, in the step (1), the mass ratio of the hydroxyethylated bisphenol a type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (25 to 90): (75-10).
In a preferred embodiment, in the step (1), the heating temperature is 40 to 130 ℃.
In a preferred embodiment, in step (2), the curing agent is at least one of diaminodiphenylmethane (DDM), 4-diaminodiphenylsulfone (DDS), isophorone diamine (IPDA), or diethyl toluene diamine (DETDA).
In a preferred embodiment, in step (4), the temperature-programmed curing parameters include: preserving heat for 2-3 h at 140-160 ℃, and preserving heat for 4-5 h at 170-190 ℃.
According to a third aspect of the invention, a temperature-responsive shape-memory epoxy resin-based composite material is provided, which comprises the following components in parts by mass:
40-90 parts of an epoxy resin matrix;
10-60 parts of a fiber reinforcement;
6.63-16.0 parts of a curing agent;
in a preferred embodiment, the epoxy resin matrix is selected from at least one of a hydroxyethylated bisphenol a type epoxy resin comprising 2 to 6 hydroxyethyl units in its molecular structure or a hydroxyethylated bisphenol fluorene type epoxy resin; the hydroxyethylated bisphenol fluorene epoxy resin takes bisphenol fluorene as a hard segment group and two hydroxyethyl groups as a soft segment group; preferably, the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (100-60): (0-40); more preferably, the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (100-70): (0 to 30).
In a preferred embodiment, the fiber reinforcement is selected from at least one of NJT300 carbon fiber plain weave, MT300 carbon fiber twill weave, TG800 carbon fiber plain weave and TG800 carbon fiber twill weave, MT800 carbon fiber plain weave or aramid fiber plain weave.
In a preferred embodiment, the curing agent is selected from at least one of diaminodiphenylmethane (DDM), 4, 4-diaminodiphenylsulfone (DDS), isophorone diamine (IPDA), or diethyl toluene diamine (DETDA).
According to a fourth aspect of the present invention, there is provided a method for preparing a temperature-responsive shape-memory epoxy resin-based composite material, as shown in fig. 1, comprising the steps of:
step (1): uniformly mixing the selected epoxy resin matrix and the curing agent in proportion;
step (2): laying fiber reinforcement bodies in a mould according to the determined laying angle and the determined sequence;
and (3): injecting the preheated epoxy resin system in the step 1 from the glue injection port at a set temperature and pressure;
and (4): and finishing the temperature programming curing process in a baking oven, a self-heating device or an autoclave and the like to prepare the shape memory epoxy resin matrix composite material.
In a preferred embodiment, the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin in the step (1) is (100 to 60): (0-40); more preferably, the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (100-70): (0 to 30).
In a preferred embodiment, in the step (1), the selected epoxy resin matrix and the curing agent are uniformly mixed in proportion at 40-90 ℃.
In a preferred embodiment, in step (1), the viscosity of the epoxy resin at 40 ℃ is 300 to 1000 mPas.
In a preferred embodiment, in the step (3), the temperature is 60 to 90 ℃ and the pressure is 0.20 to 0.60 MPa. Or the temperature is 40-80 ℃, and the pressure is-0.1 to-0.06 MPa.
In a preferred embodiment, in the step (4), the temperature-programmed curing parameters are: preserving heat for 2-3 h at 140-160 ℃, and preserving heat for 4-5 h at 170-190 ℃.
The method adopts a low-viscosity liquid molding process, can obtain shape memory composite material products with different shapes by designing and preparing molds with different structural forms, and has the advantages of simple molding process, convenient operation, no use of any solvent, environmental friendliness, good product stability, high production efficiency and easy realization of batch production.
Examples
The preparation method of the hydroxyethylated bisphenol fluorene epoxy resin in the embodiments 1 to 9 comprises the following steps: step (1): uniformly mixing 1 equivalent of fluorenyl bisphenol A polyether alcohol and 10 equivalents of propylene oxide in a solvent, and slowly heating to 50 ℃; step (2): adding 6 equal parts of the mixed liquid obtained in the step (1) into 3 equivalents of sodium hydroxide, wherein the adding time interval of each part is half an hour; and (3): the mixture in step (2) was stirred at 50 ℃ for 1 h.
Example 1
A temperature response shape memory epoxy resin is prepared by mixing 80 parts of hydroxyethylated bisphenol A type epoxy resin and 20 parts of hydroxyethylated bisphenol fluorene type epoxy resin (chemical structure diagram shown in figure 2 and infrared diagram shown in figure 3) at 100 deg.C to obtain clear and transparent shape; cooling to 80 ℃, adding 17.71 parts of diethyl toluene diamine (DETDA) curing agent, and uniformly mixing; and (3) degassing the mixture in vacuum, pouring the mixture into a preheated mold, curing the mixture in an oven for 2 hours at 150 ℃, and curing the mixture for 4 hours at 180 ℃ by gradient heating to complete the preparation of the shape memory epoxy resin.
Example 2
This example is the same as embodiment 1, except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 0: 100.
Example 3
This example is the same as embodiment 1, except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 50: 50.
Example 4
This example is the same as embodiment 1, except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 100: 0.
Example 5
A temperature response shape memory epoxy resin-based composite material is prepared by preparing an epoxy resin glue solution from hydroxyethylated bisphenol A epoxy resin, hydroxyethylated bisphenol fluorene epoxy resin and diethyl toluene diamine (DETDA) curing agent according to a mass ratio of 80:20: 17.71. Two layers of +/-45 JHT300-6K carbon fiber plain cloth are placed in a mould as a reinforcement (the mass ratio of HT300-6K carbon fiber plain cloth to an epoxy resin matrix is 10:90), the outlet is connected with vacuum, the pressure is-0.1 MPa, epoxy resin glue solution which is preheated to 50 ℃ is injected into the mould at the temperature of 50 ℃, the whole cavity is sealed and coated after the resin is filled, the resin is cured for 2h at the temperature of 150 ℃ in an oven, and the temperature is cured for 4h at the temperature of 180 ℃ to finish the preparation of the composite material by gradient heating.
Example 6This example is the same as embodiment 5 except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 0: 100.
Example 7
This example is the same as embodiment 5 except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 50: 50.
Example 8
This example is the same as embodiment 5 except that: the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is 100: 0.
Example 9
This example is the same as embodiment 5 except that: five layers of MT800-6K carbon fiber twill cloth are selected as a reinforcement, and the mold glue injection is completed under the conditions of 0.50MPa injection pressure and 80 ℃.
The shape memory epoxy resins prepared by examples 1-4 all had excellent shape memory properties, with both shape fixation and shape recovery rates greater than 99%. The shape fixation rate and the shape recovery rate of the shape memory epoxy resin prepared by the embodiment 1 are both more than 99.4%; in addition, the material has excellent mechanical performance, and the room temperature tensile strength is 67.3MPa, and the tensile modulus is 2.70 GPa.
With the increase of the content of the hydroxyethylated bisphenol fluorene epoxy resin in the shape memory epoxy resins prepared in examples 1 to 4, the proportion of the segment of the "hard segment" in the epoxy resin network increases, the rigidity is enhanced, the crosslinking density increases, the transition temperature of the shape memory epoxy resins gradually increases, and gradually increases from 87 ℃ to 166 ℃, as shown in table 1 below.
The shape memory properties of the epoxy resins prepared by examples 1-4 were thermally driven and exhibited temperature responsiveness. In addition, the same sample recovered at different recovery temperatures at different rates. The graph of the shape recovery rate of the epoxy resin prepared in example 1 as a function of the recovery time at different recovery temperatures is shown in fig. 4, in which 180 seconds are required for complete recovery of the sample at 100 ℃, 46 seconds are required at 110 ℃ and 30 seconds are required at 120 ℃, and the recovery time is gradually shortened and the recovery speed is increased as the recovery temperature is increased.
TABLE 1 shape memory Properties and transition temperature test results for shape memory epoxy resins
The transition temperature changes of the shape memory epoxy resin composites prepared by examples 5-8 were similar to the corresponding resin matrix, as shown in table 2 below. The result of the Dynamic Mechanical Analysis (DMA) test of the shape memory epoxy resin composite material prepared in example 5 is shown in fig. 5, and it can be seen that the transition temperature of the shape memory epoxy resin composite material is 113 ℃.
The epoxy resin composite materials prepared by the embodiments 5-8 also all show excellent shape memory performance, and the shape fixing rate and the shape recovery rate are both more than 90%. The composite material obtained in example 5 had a shape fixing rate of more than 96.1% at 110 ℃ and a shape recovery rate of more than 92.5%, and the shape recovery process is shown in FIG. 6, in which the test pieces gradually underwent shape recovery with time in an oil bath at 110 ℃.
The composite material prepared by the embodiment 5 also has excellent mechanical properties, wherein the tensile strength at room temperature is 94.8MPa, and the tensile modulus is 8.41GPa, and the specific data are shown in the following table 3.
TABLE 2 shape memory Properties and transition temperature test results for composites
TABLE 3 shape memory and mechanical Properties test results of the composites
| Examples | Tensile Strength (MPa) | Tensile modulus (GPa) | Shape fixation Rate (%) | Shape recovery (%) |
| Example 5 | 94.9 | 8.41 | ＞96％ | ＞99％ |
| Example 9 | 801 | 60.7 | ＞95％ | ＞99％ |
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (10)
1. The shape memory epoxy resin is characterized in that the shape memory epoxy resin is a mixture of hydroxyethylated bisphenol A type epoxy resin and hydroxyethylated bisphenol fluorene type epoxy resin in any proportion.
2. The shape memory epoxy resin according to claim 1, wherein the hydroxyethylated bisphenol a type epoxy resin contains 2 to 6 hydroxyethyl groups in its molecular structure.
3. Shape memory epoxy resin according to claim 1, characterized in that the hydroxyethylated bisphenol fluorene type epoxy resin has bisphenol fluorene as "hard segment" group and two hydroxyethyl groups as "soft segment" groups.
4. A preparation method of shape memory epoxy resin is characterized by comprising the following steps:
step (1): mixing hydroxyethylated bisphenol A epoxy resin and hydroxyethylated bisphenol fluorene epoxy resin in certain proportion and heating to clear;
step (2): adding curing agents with equal metering ratio into the mixed liquid in the step (1), and uniformly stirring until the curing agents are completely dissolved;
and (3): degassing the mixture of step (2) in vacuum, and then pouring into a preheated mold;
and (4): and finishing the temperature programming curing process in an oven, a self-heating device or an autoclave mode to prepare the shape memory epoxy resin.
5. The method for producing a shape memory epoxy resin according to claim 4, wherein in the step (1), the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is an arbitrary ratio; and/or
In the step (2), the curing agent is at least one of diaminodiphenylmethane (DDM), 4-diaminodiphenylsulfone (DDS), isophorone diamine (IPDA) or diethyl toluene diamine (DETDA); and/or
In the step (4), the programmed temperature curing parameters include: preserving heat for 2-3 h at 140-160 ℃, and preserving heat for 4-5 h at 170-190 ℃.
6. The shape memory epoxy resin-based composite material is characterized by comprising the following components in parts by mass:
40-90 parts of an epoxy resin matrix;
10-60 parts of a fiber reinforcement;
6.63-16.0 parts of a curing agent;
wherein the epoxy resin matrix is selected from at least one of hydroxyethylated bisphenol A epoxy resin or hydroxyethylated bisphenol fluorene epoxy resin, and the molecular structure of the hydroxyethylated bisphenol A epoxy resin contains 2-6 hydroxyethyl units; the hydroxyethylated bisphenol fluorene epoxy resin takes bisphenol fluorene as a hard segment group and two hydroxyethyl groups as a soft segment group; the mass ratio of the hydroxyethylated bisphenol A type epoxy resin to the hydroxyethylated bisphenol fluorene type epoxy resin is (100-60): (0-40).
7. The shape memory epoxy resin based composite material according to claim 6, wherein the fiber reinforcement is selected from at least one of NJT300 carbon fiber plain weave, MT300 carbon fiber twill weave, TG800 carbon fiber plain weave and TG800 carbon fiber twill weave, MT800 carbon fiber plain weave or aramid fiber plain weave; and/or
The curing agent is selected from at least one of diaminodiphenylmethane (DDM), 4, 4-diaminodiphenylsulfone (DDS), isophorone diamine (IPDA) or diethyl toluene diamine (DETDA).
8. A preparation method of a shape memory epoxy resin matrix composite material is characterized by comprising the following steps:
step (1): uniformly mixing the selected epoxy resin matrix and the curing agent in proportion;
step (2): laying fiber reinforcement bodies in a mould according to the determined laying angle and the determined sequence;
and (3): injecting the preheated epoxy resin system in the step 1 from the glue injection port at a set temperature and pressure;
and (4): and finishing the temperature programming curing process in a baking oven, a self-heating device or an autoclave manner to prepare the shape memory epoxy resin matrix composite material.
9. The method for preparing the shape memory epoxy resin-based composite material according to claim 8, wherein in the step (1), the viscosity of the epoxy resin at 40 ℃ is 300 to 1000 mPas.
10. The preparation method of the shape memory epoxy resin matrix composite material as claimed in claim 8, wherein in the step (3), the temperature is 60-90 ℃, and the pressure is 0.20-0.60 MPa; or the temperature is 40-80 ℃, and the pressure is-0.1 to-0.06 MPa;
in the step (4), the temperature programming curing parameters are as follows: preserving heat for 2-3 h at 140-160 ℃, and preserving heat for 4-5 h at 170-190 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080269420A1 (en) * | 2005-12-15 | 2008-10-30 | Tat Hung Tong | Shape Memory Epoxy Copolymer |
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| CN115572459A (en) * | 2022-09-05 | 2023-01-06 | 江苏科化新材料科技有限公司 | Epoxy resin material and preparation method thereof |
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