A thermoset shape memory polymer, composite material and preparation method and application thereof

Abstract

The present application relates to a kind of thermosetting shape memory polymer, composite material and its preparation method and application, belong to shape memory material technical field, the thermosetting shape memory polymer is obtained by the mixture of including styrene, acrylate monomer, free radical initiator and polyethylene glycol diacrylate is cured by heat.This application provides thermosetting shape memory polymer has excellent thermal stability and shape memory performance, can still remember initial shape at higher temperature, shape recovery rate and fixed rate can reach 99%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of shape memory materials, in particular to a thermosetting shape memory polymer, a composite material and a preparation method and application thereof. BACKGROUND

[0002] In the manufacturing industry, molds are important tools for component forming and have an irreplaceable important position. With the technical transformation of manufacturing engineering, there are higher requirements for the design and production of complex components. The traditional manufacturing technology has problems such as difficult demolding, complex design, and heavy mold self-weight, and it is difficult to realize the production of complex components with variable structure, variable curvature, and variable cross section, which seriously restricts the development of complex components.

[0003] Shape memory polymer (SMP) is an emerging intelligent material with unique shape memory effect, which can automatically return to its original shape under external stimulation, and has broad application prospects. Combining the active deformation characteristics of SMP with the manufacturing of complex components to make shape memory intelligent molds will be expected to realize the active demolding of complex components and promote the efficient and rapid production of complex components.

[0004] However, in the existing field of intelligent deformable core molds, the deformation amount of intelligent materials is limited, which is difficult to meet the deformation amount requirements of some large cavity complex components. SUMMARY

[0005] In view of one or more technical problems in the prior art, the present application provides a thermosetting shape memory polymer, a composite material and a preparation method and application thereof. The thermosetting shape memory polymer provided by the present application has excellent thermal stability and shape memory performance, and can still remember the initial shape at a higher temperature (above 200℃), and the shape recovery rate and fixation rate can reach 99%.

[0006] In a first aspect, the present application provides a thermosetting shape memory polymer, which is obtained by heat curing a mixture comprising styrene, an acrylate monomer, a free radical initiator and polyethylene glycol diacrylate.

[0007] Preferably, the styrene is 20-90 parts by weight, the acrylate monomer is 10-80 parts by weight, the free radical initiator is 0.5-3 parts by weight, and the polyethylene glycol diacrylate is 0.5-10 parts by weight.

[0008] Preferably, the acrylate monomer includes but is not limited to one or more of methyl acrylate, butyl acrylate, methyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, and octadecyl acrylate.

[0009] The radical initiator includes, but is not limited to, one or more of azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxide, dibenzoyl peroxide, azobisisoheptyl nitrile; and / or

[0010] The number average molecular weight of the polyethylene glycol diacrylate is 100-3000.

[0011] The present application provides, in a second aspect, a thermosetting shape memory composite material, comprising the thermosetting shape memory polymer and the elastic fiber material according to the first aspect.

[0012] Preferably, the volume fraction of the elastic fiber material in the thermosetting shape memory composite material is not more than 30%.

[0013] Preferably, the elastic fiber material is one or more of an elastic fiber layer, an elastic fiber fabric; preferably, the elastic fiber in the elastic fiber material is selected from one or more of spandex fiber, nylon fiber, polypropylene fiber, polyethylene fiber, polyurethane fiber.

[0014] The present application provides, in a third aspect, a preparation method of the thermosetting shape memory composite material according to the second aspect, the preparation method comprising:

[0015] Mixing styrene, acrylate monomer, radical initiator and polyethylene glycol diacrylate to obtain a premix;

[0016] Mixing the elastic fiber material after layering with the premix, and performing thermosetting to obtain the thermosetting shape memory composite material.

[0017] Preferably, the laying angle of the elastic fiber in the elastic fiber material is -180°-180°, preferably -45°-45°.

[0018] Preferably, the temperature of the thermosetting is 60-120℃, and the time is 7-24h.

[0019] The present application provides, in a fourth aspect, an application of the thermosetting shape memory composite material according to the second aspect, for the field of intelligent core mold.

[0020] Compared with the prior art, the present application has at least the following beneficial effects:

[0021] The present application uses styrene and acrylate monomers as polymerization monomers, and through rigid-flexible coupling molecular structure design, the molecular chain segments in the thermosetting shape memory polymer network are flexibly adjusted, so that the thermosetting shape memory polymer has shape memory characteristics and large deformation capability. The polymerization monomers are polymerized under the action of a free radical initiator and a crosslinking agent to form a thermosetting shape memory polymer with a three-dimensional network molecular structure. Compared with thermoplastic or semi-interpenetrating network shape memory polymers, the thermosetting shape memory polymer has better thermal stability and shape memory performance, and can still remember the initial shape at a higher temperature (above 200℃), and the shape recovery rate and fixing rate can reach 99%.

[0022] The present application obtains a thermosetting shape memory composite material by compounding a shape memory polymer matrix with an elastic fiber material, wherein the elastic fiber has good conformability and can adapt to the deformation of the shape memory polymer matrix, effectively inhibits the crack propagation of the shape memory polymer matrix, and improves the deformation capability of the composite material without limiting the deformation capability of the shape memory polymer matrix. The thermosetting shape memory composite material provided by the present application has high breaking elongation, shape fixing rate and shape recovery rate at deformation temperature, and can meet the requirements of a core mold for forming a large cavity complex component. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0024] Figure 1 is a physical diagram of the large deformation recovery process of the thermosetting shape memory polymer provided by embodiment 1 of the present application;

[0025] Figure 2 is a shape memory cycle curve of the thermosetting shape memory polymer provided by embodiment 1 of the present application;

[0026] Figure 3 is a DMA curve of the shape memory polymer provided by embodiment 1, embodiment 2 and comparative example 1 of the present application;

[0027] Figure 4 is a limit strain columnar diagram of the shape memory polymer provided by comparative example 1, embodiment 1, embodiment 2 and embodiment 5 of the present application at Tg-20℃;

[0028] Figure 5 is a thermogravimetric analysis curve of the shape memory polymer provided by embodiment 1, embodiment 2 and comparative example 1 of the present application;

[0029] Figure 6 is a DSC test curve of the shape memory polymer provided by the embodiment 1, the embodiment 3 and the embodiment 4 of the present application;

[0030] Figure 7 is a DMA curve of the thermosetting shape memory composite material provided by the embodiment 5 of the present application;

[0031] Figure 8 is a shape memory cycle curve of the thermosetting shape memory composite material provided by the embodiment 5 of the present application. DETAILED DESCRIPTION

[0032] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0033] The present application provides, in a first aspect, a thermosetting shape memory polymer, which is obtained by heat curing a mixture comprising styrene, an acrylate monomer, a free radical initiator and polyethylene glycol diacrylate.

[0034] The present application uses styrene and an acrylate monomer as polymerization monomers, and adjusts the flexibility of the molecular chain segments in the thermosetting shape memory polymer network through rigid-flexible coupling molecular structure design, so that the thermosetting shape memory polymer has shape memory characteristics and large deformation capability. The polymerization monomers are polymerized under the action of a free radical initiator and a crosslinking agent to form a thermosetting shape memory polymer with a three-dimensional network molecular structure. Compared with thermoplastic or semi-interpenetrating network shape memory polymers, the thermosetting shape memory polymer has better thermal stability and shape memory performance, and can still remember the initial shape at a higher temperature (above 200℃), and the shape recovery rate and fixation rate can reach 99%.

[0035] According to some preferred embodiments, the styrene is 20-90 parts by weight (for example, it can be 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts or 90 parts), the acrylate monomer is 10-80 parts by weight (for example, it can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts or 80 parts), the free radical initiator is 0.5-3 parts by weight (for example, it can be 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts), and the polyethylene glycol diacrylate is 0.5-10 parts by weight (for example, it can be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts).

[0036] According to some preferred embodiments, the acrylate monomer includes, but is not limited to, one or more of methyl acrylate, butyl acrylate, methyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, and stearyl acrylate;

[0037] The free radical initiator includes, but is not limited to, one or more of azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxide, dibenzoyl peroxide, and azobisisoheptane nitrile; and / or

[0038] The number average molecular weight of the polyethylene glycol diacrylate is 100-3000.

[0039] The present application provides, in a second aspect, a thermosetting shape memory composite material, comprising the thermosetting shape memory polymer and the elastic fiber material according to the first aspect.

[0040] The present application provides a thermosetting shape memory composite material by compounding a shape memory polymer matrix with an elastic fiber material, wherein the elastic fiber has good shape-following ability and can adapt to the deformation of the shape memory polymer matrix, effectively inhibits the crack propagation of the shape memory polymer matrix without limiting the deformation ability of the shape memory polymer matrix, and improves the deformation ability of the composite material. The thermosetting shape memory composite material provided by the present application has high breaking elongation, shape fixation rate and shape recovery rate at the deformation temperature, and can meet the requirements of core mold for forming large cavity complex components.

[0041] It should be noted that the most suitable deformation temperature range of the thermosetting shape memory polymer and the thermosetting shape memory composite material of the present application is Tg-30℃ to Tg+30℃, wherein Tg is the glass transition temperature.

[0042] According to some preferred embodiments, the volume fraction of the elastic fiber material in the thermosetting shape memory composite material is not greater than 30%.

[0043] The volume fraction of the elastic fiber material in the thermosetting shape memory composite material of the present application should not be too large. The inventors have found that if the volume fraction of the elastic fiber material is too large, it will affect the continuity of the shape memory polymer matrix, and further negatively affect the shape memory performance of the composite material, and even lose the shape memory performance.

[0044] According to some preferred embodiments, the elastic fiber material is one or more of an elastic fiber layer and an elastic fiber fabric; preferably, the elastic fiber in the elastic fiber material is selected from one or more of spandex fiber, polyurethane fiber, polypropylene fiber, and polyethylene fiber.

[0045] The application provides a preparation method of the thermosetting shape memory composite material in the third aspect, and the preparation method comprises the following steps:

[0046] The styrene, the acrylate monomer, the free radical initiator and the polyethylene glycol diacrylate are uniformly mixed to obtain a premix;

[0047] The elastic fiber material is layered and mixed with the premix, and then is heat-cured to obtain the thermosetting shape memory composite material.

[0048] The preparation method of the thermosetting shape memory composite material is simple, and the prepared thermosetting shape memory composite material has high breaking elongation, shape fixation rate and shape recovery rate, can meet the use requirements of a deformable intelligent core mold and is used for forming a component with a large cavity and a complex structure.

[0049] According to some preferred embodiments, the laying angle of the elastic fiber in the elastic fiber material is -180°-180° (for example, can be -180°, -150°, -120°, -90°, -60°, -30°, 0°, 30°, 60°, 90°, 120°, 150° or 180°), preferably -45°-45° (for example, can be -45°, -30°, 0°, 30° or 45°).

[0050] According to some preferred embodiments, the temperature of the heat curing is 60-120 ℃ (for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃), and the time is 7-24 h (for example, 7 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 24 h).

[0051] The application provides an application of the thermosetting shape memory composite material in the fourth aspect, which is used in the field of intelligent core molds.

[0052] The thermosetting shape memory composite material has high breaking elongation, shape fixation rate and shape recovery rate, can meet the use requirements of a deformable intelligent core mold and is used for forming a component with a large cavity and a complex structure.

[0053] The forming mode of the intelligent core mold component formed by the thermosetting shape memory composite material comprises one or more of die forming, blow molding and the like.

[0054] In order to more clearly illustrate the technical solutions and advantages of the present application, the present application will be further described below in conjunction with examples. The sources of the reagents used in the examples and comparative examples of the present application are not specifically limited and can be directly purchased or synthesized by the present application. The parts in the following examples and comparative examples of the present application are parts by weight.

[0055] Example 1

[0056] A preparation method of a thermosetting shape memory polymer, comprising: placing 80 parts of styrene, 20 parts of butyl acrylate, 3 parts of polyethylene glycol diacrylate 200, and 2 parts of benzoyl peroxide in a beaker, stirring for 30 min to ensure uniform mixing, to obtain a premix. The surface of the mold is coated with a release agent and dried, and the operation is repeated three times. The above premix is poured into the mold, and heat curing is performed according to the following curing program: first at 70℃ for 2h, then at 90℃ for 2h, and finally at 120℃ for 3h, to obtain a thermosetting shape memory polymer.

[0057] As shown in Figure 1 , the thermosetting shape memory polymer prepared in this example can realize the recovery process of large deformation at 90℃, which intuitively shows that the thermosetting shape memory polymer prepared in this example has large deformation and shape memory capability.

[0058] As shown in Figure 2 , the thermosetting shape memory polymer prepared in this example still has a shape fixation rate and a shape recovery rate of 99% after four shape memory cycles, and has good shape memory performance. It should be noted that, Figure 2 The horizontal coordinate is time, and from left to right, the vertical coordinates are temperature (black), strain (red), and stress (blue).

[0059] Example 2

[0060] A preparation method of a thermosetting shape memory polymer, comprising: placing 80 parts of styrene, 20 parts of butyl acrylate, 6 parts of polyethylene glycol diacrylate 400, and 2 parts of benzoyl peroxide in a beaker, stirring for 30 min to ensure uniform mixing, to obtain a premix. The surface of the mold is coated with a release agent and dried, and the operation is repeated three times. The above premix is poured into the mold, and heat curing is performed according to the following curing program: first at 70℃ for 2h, then at 90℃ for 2h, and finally at 120℃ for 3h, to obtain a thermosetting shape memory polymer.

[0061] Comparative Example 1

[0062] The same as Example 1, except that the crosslinking agent is divinylbenzene.

[0063] The shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 are made into test pieces to determine the DMA curves thereof, as shown in Fig. 1, wherein the abscissa represents temperature and the ordinate represents tangent of loss angle. The glass transition temperatures (Tg) of the shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 are 88.1℃, 81.2℃ and 90.3℃, respectively. It can be seen that, compared with Comparative Example 1 using divinyl benzene as the crosslinking agent, the glass transition temperature (Tg) of the shape memory polymer can be reduced by using polyethylene glycol diacrylate as the crosslinking agent in Example 1 and Example 2. Figure 3 As shown in Fig. 1, the abscissa represents temperature and the ordinate represents tangent of loss angle. The glass transition temperatures (Tg) of the shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 are 88.1℃, 81.2℃ and 90.3℃, respectively. It can be seen that, compared with Comparative Example 1 using divinyl benzene as the crosslinking agent, the glass transition temperature (Tg) of the shape memory polymer can be reduced by using polyethylene glycol diacrylate as the crosslinking agent in Example 1 and Example 2.

[0064] The shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 are made into test pieces (with a size of 6*80*2mm) to determine the deformation capacity of the shape memory polymers (with a gauge length of 40mm and a stretching rate of 4mm / min), as shown in Fig. 2, wherein the ordinate represents strain (elongation at break). The elongation at break of the shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 at the deformation temperature (Tg-20℃) is 370.74%, 337.47% and 242.55%, respectively. It can be seen that, compared with Comparative Example 1 using divinyl benzene as the crosslinking agent, the deformation capacity of the shape memory polymer can be obviously improved by using polyethylene glycol diacrylate as the crosslinking agent in Example 2 and Example 3. Figure 4 As shown in Fig. 2, the ordinate represents strain (elongation at break). The elongation at break of the shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 at the deformation temperature (Tg-20℃) is 370.74%, 337.47% and 242.55%, respectively. It can be seen that, compared with Comparative Example 1 using divinyl benzene as the crosslinking agent, the deformation capacity of the shape memory polymer can be obviously improved by using polyethylene glycol diacrylate as the crosslinking agent in Example 2 and Example 3.

[0065] The shape memory polymers prepared in Example 1, Example 2 and Comparative Example 1 are subjected to thermogravimetric analysis test, as shown in Fig. 3. It can be seen that the weight loss of the shape memory polymer at 300℃ is very low, and the temperature resistance performance is good. Figure 5 As shown in Fig. 3, the weight loss of the shape memory polymer at 300℃ is very low, and the temperature resistance performance is good.

[0066] Example 3

[0067] A preparation method of a thermosetting shape memory polymer, comprising: placing 75 parts of styrene, 25 parts of butyl acrylate, 3 parts of polyethylene glycol diacrylate 200 and 2 parts of benzoyl peroxide in a beaker, stirring for 30min to ensure uniform mixing, to obtain a premix. The surface of the mold is smeared with release agent and dried, and the operation is repeated three times. The above premix is poured into the mold, and heat curing is performed according to the following curing program: first, heat preservation at 70℃ for 2h, then heat preservation at 90℃ for 2h, and finally heat preservation at 120℃ for 3h, to obtain the thermosetting shape memory polymer.

[0068] Example 4

[0069] A method for preparing a thermosetting shape memory polymer includes: placing 67 parts styrene, 33 parts butyl acrylate, 3 parts polyethylene glycol diacrylate 200, and 2 parts benzoyl peroxide in a beaker and stirring for 30 minutes to ensure uniform mixing, thereby obtaining a premix. Applying a release agent to the surface of a mold and allowing it to dry, repeating this process three times. Pouring the premix into the mold and thermosetting it according to the following curing procedure: first holding at 70°C for 2 hours, then at 90°C for 2 hours, and finally at 120°C for 3 hours, to obtain the thermosetting shape memory polymer.

[0070] Depend on Figure 6 It can be seen that the glass transition temperatures (Tg) of the shape memory polymers obtained in Examples 1, 3, and 4 of this invention are 77.5℃, 69.7℃, and 57.6℃, respectively. It is evident that the glass transition temperature decreases significantly with increasing butyl acrylate content in the polymer monomer. It should be noted that the horizontal axis in the figure represents temperature, and the vertical axis represents heat flux. Figure 3 and Figure 6 The glass transition temperature varies depending on the testing method used in Example 1.

[0071] Example 5

[0072] A method for preparing a thermosetting shape memory composite material includes: placing 80 parts styrene, 20 parts butyl acrylate, 3 parts polyethylene glycol diacrylate, and 2 parts benzoyl peroxide in a beaker and stirring for 30 minutes to ensure uniform mixing, thereby obtaining a premix. Applying a release agent to the surface of a mold and allowing it to dry, repeating this process three times. Laying and fixing a spandex-nylon blended fiber mesh in the mold, wherein the fiber laying angles in the spandex-nylon blended fiber mesh are -45° and +45° (i.e., the warp and weft directions are perpendicular), wherein spandex accounts for 13.6 wt% and nylon 83.4 wt% of the spandex-nylon blended fiber mesh.

[0073] The above premix was poured into a mold with a spandex-nylon blended fiber mesh fabric laid on it, and thermosetting was carried out according to the following curing procedure: first, it was kept at 70°C for 2 hours, then at 90°C for 2 hours, and finally at 120°C for 3 hours to obtain a thermosetting shape memory polymer composite material, wherein the spandex-nylon blended fiber mesh fabric accounted for 9.6% of the volume fraction of the composite material.

[0074] like Figure 7 As shown, the thermosetting shape memory composite material prepared in this embodiment contains two phases: a shape memory polymer matrix and elastic fibers, resulting in two peaks in the curve. However, the deformability of the shape memory composite material is limited by the shape memory polymer matrix. Therefore, the peak corresponding to the shape memory polymer matrix (i.e., 76.4℃) is used as the Tg of the shape memory composite material. It should be noted that... Figure 7The horizontal coordinate is temperature, and the vertical coordinate is the storage modulus (black) and the loss tangent (blue) from left to right. The elongation at break of the thermosetting shape memory composite material prepared in the embodiment can reach 376% (the gauge length is 10 mm) at the deformation temperature (56℃), as shown in Figure 4 .

[0075] As shown in Figure 8 , the shape fixation rate and the shape recovery rate of the thermosetting shape memory composite material prepared in the embodiment can still reach 99% after four shape memory cycles, and the material has good shape memory performance. It should be noted that, Figure 8 The horizontal coordinate is time, and the vertical coordinate is the temperature (black), the strain (red) and the stress (blue) from left to right.

[0076] Comparative Example 2

[0077] The embodiment is basically the same as Example 5, except that the spandex-polyamide blended fiber mesh cloth is replaced by a glass fiber-carbon fiber blended fiber mesh cloth.

[0078] The use of the glass fiber-carbon fiber blended fiber mesh cloth seriously limits the deformation ability of the composite material.

[0079] Comparative Example 3

[0080] The embodiment is basically the same as Example 5, except that the volume fraction of the spandex-polyamide blended fiber mesh cloth in the composite material is 50%. Due to the excessive fiber content, the polymer matrix resin can only immerse the fibers, and after curing, the situation of partial fiber bare leakage occurs, which affects the continuity of the matrix, and thus the shape memory performance cannot be shown.

[0081] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement to part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A thermoset shape memory composite material, characterized in that, The thermosetting shape memory polymer is obtained by thermal curing of a mixture comprising styrene, acrylate monomer, free radical initiator and polyethylene glycol diacrylate; the elastic fiber material is spandex-nylon blended fiber mesh; the volume fraction of the elastic fiber material in the thermosetting shape memory composite material is not more than 30%; the thermosetting shape memory composite material has high elongation at break at deformation temperature, shape fixation rate and shape recovery rate.

2. The thermoset shape memory composite of claim 1, wherein, The raw materials for preparing the thermosetting shape memory polymer include the following components by weight fraction: Styrene is 20-90 parts, acrylate monomer is 10-80 parts, free radical initiator is 0.5-3 parts, and polyethylene glycol diacrylate is 0.5-10 parts.

3. The thermoset shape memory composite of claim 1, wherein, The acrylate monomer includes one or more of methyl acrylate, butyl acrylate, methyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, and octadecyl acrylate; The free radical initiator includes one or more of azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxide, dibenzoyl peroxide, and azobisisoheptyl nitrile; and / or The number average molecular weight of polyethylene glycol diacrylate is 100-3000.

4. A process for the production of the thermoset shape memory composite material according to any one of claims 1 to 3, characterized in that, The preparation method comprises: Mixing styrene, acrylate monomer, free radical initiator, and polyethylene glycol diacrylate to obtain a premix; After the elastic fiber material is laid, it is mixed with the premix, and then thermally cured to obtain the thermosetting shape memory composite material.

5. The production method according to claim 4, characterized by, The laying angle of the elastic fiber in the elastic fiber material is -180°-180°.

6. The production method according to claim 5, wherein The laying angle of the elastic fiber in the elastic fiber material is -45°-45°.

7. The preparation method according to claim 4, characterized in that, The temperature of the thermal curing is 60-120°C, and the time is 7-24h.

8. Use of the thermoset shape memory composite material according to any one of claims 1 to 3, characterized in that, For the field of intelligent core mold.

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