CN114806166A - Triple shape memory cyanate and preparation method thereof - Google Patents
Triple shape memory cyanate and preparation method thereof Download PDFInfo
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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Abstract
The invention provides a triple shape memory cyanate ester and a preparation method thereof, belonging to the technical field of shape memory polymer synthesis. The triple shape memory cyanate comprises the following components in parts by weight: 30-40 parts of cyanate ester prepolymer, 10-20 parts of epoxy resin, 10-20 parts of epoxy acrylate, 20-30 parts of acrylate and 2-5 parts of photoinitiator; the cyanate ester prepolymer and the epoxy resin are used for forming a thermally initiated polymer network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymer network under photo initiation. The interpenetrating network structure is formed by utilizing the thermal initiation polymerization network structure and the photo initiation polymerization network, and the reversible phase and the fixed phase of the two network structures are different, and the glass transition temperature peak distance is long, so that the mutual interference in the multiple shape recovery processes is small, the excellent triple shape memory performance is ensured, and the selective driving deformation and the selective shape recovery can be realized.
Description
Technical Field
The invention relates to the technical field of shape memory polymer synthesis, in particular to a triple shape memory cyanate ester and a preparation method thereof.
Background
Shape Memory Polymers (SMPs) are novel intelligent materials with Shape memory capacity, namely, a temporary Shape is endowed to the SMPs at the glass transition temperature, the temporary Shape is fixed by cooling, and the smp can be restored to the original Shape after being stimulated by the outside, so that the smp has a memory function on the original Shape. Compared with shape memory alloy and shape memory ceramic, the shape memory polymer has the advantages of low density, large recoverable deformation amount, easy processing and forming, adjustable deformation temperature and the like, so the shape memory polymer has wide application prospect in the fields of flexible electronics, biomedicine, aerospace and the like. The shape memory polymer materials developed at present are mainly dual shape memory polymers, and only have one reversible phase and Glass transition temperature (T) g ) In the shape memory process, only one deformation stage and one recovery stage are provided, and the application of the method has certain limitation in the face of increasingly complex intelligent scenes. Therefore, developing a new memory storage method and implementing multiple shape memories are important to meet the complex requirements of the future intelligent field.
In order to realize such shape memory characteristics, multiple SMPs such as triple SMPs can change from an initial shape to a temporary shape I, and then from the temporary shape I to a temporary shape II in a deformation and fixation process, the multiple shape memory polymer should have two or more glass transition temperatures, and then a plurality of deformation stages and recovery stages respectively occur in a shape memory process to perform a complex deformation response. The complex shape memory effect makes it possible to apply multiple shape memory polymers in many fields. The currently reported triple SMPs are generally prepared by blending two resins or by polymer grafting. When the two resins are blended to prepare the triple SMPs, the two resins need to have good compatibility, the curing mode is single, and the two resins are generally thermally cured, so that the types of the selectable resins are greatly limited. When the SMPs are prepared by polymer grafting, the preparation method is complicated and has a plurality of influencing factors, and factors such as molecular structure, molecular weight, grafting success rate and the like can influence the triple shape memory performance of the resin, so that the glass transition temperature range of the resin is narrow or the separation of glass transition peaks is not obvious, the shape recovery of two temporary shapes interferes with each other, and the subsequent application is not facilitated.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a triple shape memory cyanate ester and a method for preparing the same.
In order to achieve the purpose, the invention is specifically realized by the following technical scheme:
the invention provides a triple shape memory cyanate ester, which comprises the following components in parts by weight: 30-40 parts of cyanate ester prepolymer, 10-20 parts of epoxy resin, 10-20 parts of epoxy acrylate, 20-30 parts of acrylate and 2-5 parts of photoinitiator; the cyanate ester prepolymer and the epoxy resin are used for forming a thermally initiated polymerization network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymerization network under photo initiation.
Further, the triple shape memory cyanate ester comprises the following components in parts by weight: 32-38 parts of cyanate ester prepolymer, 12-18 parts of epoxy resin, 14-18 parts of epoxy acrylate, 24-28 parts of acrylate and 3-5 parts of photoinitiator. Still further, comprising: 34-36 parts of cyanate ester prepolymer, 16-18 parts of epoxy resin, 16-18 parts of epoxy acrylate, 24-26 parts of acrylate and 4-5 parts of photoinitiator.
Further, the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving a cyanate monomer at the temperature of 110-120 ℃, then continuously heating and stirring for 180-220h, and cooling to room temperature to obtain the cyanate prepolymer.
Further, the cyanate ester monomer is bisphenol a cyanate ester.
Further, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, cyanuric acid epoxy resin, novolac epoxy resin and hydantoin epoxy resin.
Further, the epoxy acrylate is selected from one or more of bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cyanuric acid epoxy acrylate, phenol aldehyde epoxy acrylate and hydantoin epoxy acrylate.
Further, the acrylate is selected from one or more of polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.
Further, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
Further, the glass transition temperature of the thermal initiation polymerization network is 160-235 ℃, and the glass transition temperature of the photoinitiation polymerization network is 80-105 ℃.
In addition, the invention provides a preparation method of the triple shape memory cyanate ester, which comprises the following steps:
s1, uniformly mixing the cyanate ester prepolymer, the epoxy resin, the epoxy acrylate, the acrylate and the photoinitiator in parts by weight to obtain printable ink;
s2, printing and molding the printable ink by adopting a photocuring printing technology;
and S3, sequentially carrying out ultraviolet irradiation and heating treatment on the printed and molded object to obtain the triple shape memory cyanate.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes cyanate prepolymer and epoxy resin to generate polymerization reaction under thermal initiation to generate thermal initiation polymerization network structure, utilizes epoxy acrylate and acrylate to generate polymerization reaction under photo initiation to generate photo initiation polymerization network, the thermal initiation polymerization network structure and the photo initiation polymerization network are mutually interpenetrated to form interpenetrating network, because reversible phase and fixed phase of the thermal initiation polymerization network and the photo initiation polymerization network are different, glass transition temperature range of the resin is wider and glass transition temperature peak distance is far, thus mutual interference of multiple shape recovery processes is small, excellent triple shape memory performance is ensured, and selective drive deformation and selective shape recovery can be realized. In addition, the interpenetrating networks are constructed through different resin types and different curing modes, so that the polymer has more flexible design and more excellent performance.
2. According to the invention, an interpenetrating network structure is formed by the thermal initiation polymerization network and the photo initiation polymerization network, so that the mechanical property is favorably enhanced, the tensile strength of the triple shape memory cyanate ester is up to more than 60MPa, the elongation at break is more than 10%, the shape memory fixing rate is more than 96%, and the shape memory recovery rate is more than 93%.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of a cyanate ester prepolymer under different heating times in the embodiment of the present invention;
FIG. 2 is a dynamic mechanical analysis graph of the triple shape memory cyanate ester of example 1 of the present invention;
FIG. 3 is a diagram showing the triple shape memory deformation process of the triple shape memory cyanate ester of example 1 of the present invention;
FIG. 4 is a diagram illustrating the triple shape memory recovery process of the triple shape memory cyanate ester according to example 1 of the present invention;
FIG. 5 is a graph showing the shape memory cycle test of the triple shape memory cyanate ester of example 1;
FIG. 6 is a graph showing the mechanical properties of the triple shape memory cyanate ester of example 1 of the present invention;
FIG. 7 is a dynamic mechanical analysis graph of the triple shape memory cyanate ester of example 2 of the present invention;
FIG. 8 is a graph showing the shape memory cycle test of the triple shape memory cyanate ester of example 2 of the present invention;
fig. 9 is a mechanical property test chart of the triple shape memory cyanate ester of example 2 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In addition, the terms "comprising," "including," and "having" are intended to be non-limiting, i.e., other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents are commercially available unless otherwise specified.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in the present invention are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The embodiment of the invention provides a triple shape memory cyanate ester, which comprises the following components in parts by weight: 30-40 parts of cyanate ester prepolymer, 10-20 parts of epoxy resin, 10-20 parts of epoxy acrylate, 20-30 parts of acrylate and 2-5 parts of photoinitiator; the cyanate ester prepolymer and the epoxy resin are used for forming a thermally initiated polymerization network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymerization network under photo initiation.
In the invention, the cyanate prepolymer is a main material for thermal initiation polymerization, and self-polymerization reaction can occur when cyanate is heated to generate triazine ring network crosslinking points, but the generated 1,3, 5-triazine ring structure is highly symmetrical, and has large brittleness and poor toughness. The epoxy resin is used as a modifier of cyanate ester, is used for modifying a cyanate ester network structure, reduces the crosslinking degree of triazine ring, and enhances the toughness of the cyanate ester. Therefore, the cyanate ester prepolymer and the epoxy resin will generate polymerization reaction under thermal initiation, and generate a thermal initiation polymerization network structure with good shape memory performance. The epoxy acrylate and the acrylate both contain allyl active groups and are main materials for photo-initiated polymerization, and under the irradiation of ultraviolet light, the photo-initiator generates active free radicals to induce polymerization reaction. Because the acrylate and the epoxy acrylate are micromolecular substances, when the acrylate and the epoxy acrylate are respectively polymerized into a network structure independently, the network structure is single in unit, the network structure is regular and compact, the toughness is extremely poor, and the shape memory performance is not facilitated. Therefore, the invention adapts the epoxy acrylate and the acrylic ester according to a certain proportion, and the polymerization reaction is carried out under the photo-initiation to form an irregular photo-initiation polymerization network structure, thereby improving the mechanical property of the photo-initiation polymerization network structure. In addition, the acrylate can also be used as a small molecular reactive diluent for adjusting the viscosity of the ink and enhancing the printability of the ink and the matching property with a photocuring printer.
The shape memory property depends on the polymer molecular network structure, wherein the network cross-linking points are fixed phases, and the molecular chain segments between the cross-linking points are reversible phases. When the material is heated to the glass transition temperature, external force is applied to extend the molecular chain, the temperature is reduced to room temperature, the molecular chain stores potential energy, and the macroscopic appearance is that the shape is fixed; and heating to the glass transition temperature again, retracting the molecular chain, drawing the cross-linking point to return to the original state, and macroscopically expressing the shape return. The thermal initiation polymerization network and the photo initiation polymerization network generated in the invention have different molecular structures and thermodynamic properties, specifically, reversible phases and fixed phases of the two network structures are different, and the two network structures have two glass transition temperatures, the thermal initiation polymerization network formed by the cyanate ester prepolymer and the epoxy resin has high structural strength and high glass transition temperature, and the photo initiation polymerization network formed by the epoxy acrylate and the acrylic ester has low strength and low glass transition temperature; the glass transition temperature peak distance of the two network structures is far, so that the mutual interference of multiple shape recovery processes is small, the excellent triple shape memory performance is further ensured, and the selective driving deformation and the selective shape recovery can be realized. The interpenetrating networks are constructed through different resin types and different curing modes, so that the polymer has more flexible design and more excellent performance. In addition, the interpenetrating of the thermal initiation polymerization network and the photoinitiation polymerization network has synergistic effect on the mechanical property of the resin by forming an interpenetrating network structure, the tensile strength of the triple shape memory cyanate ester is up to more than 60MPa, the elongation at break is more than 10%, the shape memory fixing rate is more than 96%, and the shape memory recovery rate is more than 93%.
The glass transition temperature of the thermal initiation polymerization network is 160-235 ℃, and the glass transition temperature of the photo initiation polymerization network is 80-105 ℃.
The larger the difference between the glass transition temperatures of the two network structures is, the longer the distance between the two glass transition temperature peaks is, the smaller the mutual interference of the two shape recoveries is, and the better the triple shape memory performance is. When the epoxy resin is used for modifying cyanate ester, if the addition amount is too high, the generation amount of triazine ring is greatly reduced, the strength of the thermally-initiated polymerization network is reduced, and the glass transition temperature is reduced. The epoxy acrylate and the acrylate form a photoinitiated polymerization network, and when the addition amount of the acrylate is too high, the network structure is large in brittleness and poor in mechanical property, and the glass transition temperature is slightly increased. In the above case, the peak distances of the two glass transition temperatures become small, and the glass transition temperature ranges overlap, which is not favorable for the triple shape memory performance. Therefore, preferably, the triple shape memory cyanate ester comprises the following components in parts by weight: 32-38 parts of cyanate ester prepolymer, 12-18 parts of epoxy resin, 14-18 parts of epoxy acrylate, 24-28 parts of acrylate and 3-5 parts of photoinitiator. More preferably, it comprises: 34-36 parts of cyanate ester prepolymer, 16-18 parts of epoxy resin, 16-18 parts of epoxy acrylate, 24-26 parts of acrylate and 4-5 parts of photoinitiator.
Optionally, the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving a cyanate monomer at the temperature of 110-120 ℃, then continuously heating and stirring for 180-220h, and cooling to room temperature to obtain the cyanate prepolymer. FIG. 1 shows the morphology of cyanate ester prepolymers at different heating times.
Optionally, the cyanate ester monomer is bisphenol a cyanate ester.
Optionally, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, cyanuric acid epoxy resin, novolac epoxy resin, and hydantoin epoxy resin.
Optionally, the epoxy acrylate is selected from one or more of bisphenol a epoxy acrylate, bisphenol F epoxy acrylate, cyanuric acid epoxy acrylate, novolac epoxy acrylate, and hydantoin epoxy acrylate.
Optionally, the acrylate is selected from one or more of polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.
Optionally, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and the photoinitiator generates active free radicals to induce the polymerization reaction of the acrylate under ultraviolet irradiation.
Another embodiment of the present invention provides a method for preparing the triple shape memory cyanate ester, including the following steps:
s1, preparing printable ink: uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylate and photoinitiator in parts by weight to prepare printable ink;
s2, photocuring, printing and forming: printing and molding the printable ink by adopting a photocuring printing technology;
s3, constructing an interpenetrating network: and (3) sequentially carrying out ultraviolet irradiation and heating treatment on the printed and molded object to obtain the triple shape memory cyanate.
The preparation method of the triple shape memory cyanate ester is the same as the advantages of the triple shape memory cyanate ester compared with the prior art, and the details are not repeated herein. The invention adopts the photo-curing printing combined with a photo-thermal two-stage curing method, i.e. photoThe curing printing can realize the integrated rapid molding of a complex structure and the primary formation of a photoinitiated polymerization network structure, and then ultraviolet light is adopted for irradiation to carry out light post-curing so as to improve the printing efficiency and strengthen the photoinitiated polymerization network structure. Finally, the mechanical property of the material is further improved by heat treatment and solidification, and high T is generated g By increasing the double T g The difference between the two is beneficial to improving the triple shape memory performance.
Internal stress is generated when the heating treatment is carried out for curing, and the influence caused by the internal stress is weakened through precuring. Specifically, the pre-curing treatment adopts a gradient temperature rise mode, and comprises the following steps: the temperature is kept at 150 ℃ for 3h and 180 ℃ for 3h, the temperature for fast curing and crosslinking of cyanate is above 210 ℃, very slow curing and crosslinking reaction is carried out at 150 ℃ and 180 ℃, the activity of molecular chains at high temperature is higher, and the cyanate ester can be adjusted to a position with low internal stress to relieve the influence caused by the internal stress.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
Example 1
A triple shape memory cyanate ester comprises the following components in parts by weight: 30 parts of cyanate ester prepolymer, 15 parts of bisphenol A epoxy resin, 20 parts of bisphenol A epoxy acrylate, 30 parts of polyethylene glycol diacrylate and 5 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide;
the preparation method comprises the following steps:
s1, preparing printable ink: uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylate and photoinitiator in parts by weight to prepare printable ink;
the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving cyanate ester monomer at 120 ℃, then slowly stirring by magnetic force, uninterruptedly heating and stirring for 192h, and cooling to room temperature;
s2, photocuring, printing and forming: printing and molding printable ink by using a photocuring printer, wherein a hexapetalous flower structure is obtained by printing in the example;
s3, constructing an interpenetrating network: and (3) sequentially carrying out ultraviolet irradiation on the printed and molded object for 60min and heating to 180 ℃ for constant temperature treatment for 3h to obtain the triple shape memory cyanate.
The dynamic mechanical analysis of the triple shape memory cyanate prepared in this example is shown in fig. 2, wherein the abscissa of the graph is temperature, the ordinate of the left side is Storage modulus (Storage modulus), and the ordinate of the right side is mechanical loss (Tan Delta), which shows that the triple shape memory cyanate has two glass transition temperatures, wherein T is T g 1＝102℃，T g 2 ═ 202 ℃, and the two glass transition temperature peaks were clearly separated and the ranges overlapped less, indicating that they had excellent triple shape memory properties.
An example of a triple shape memory deformation process is as follows: heating the triple shape memory cyanate to T g 2 above, applying external force to realize the deformation of 1,3 and 5 petals, or deforming one or more other petals, and cooling to T g At a temperature of 2 ℃ and T g Above 1 deg.C, external force is applied to deform petals 2,4, and 6 (see FIG. 3). At T g Petals (2, 4, 6) deformed at 1 temperature may be at T g Shape recovery at 1 deg.C or above, and may be at T g 2 temperature above, recovering shape at T g Petals (1, 3, 5) deformed at a temperature of more than 2 ℃ can only be T g 2 deg.c or more (see fig. 4), whereby selective deformation and selective shape recovery can be achieved.
In addition, shape memory properties were characterized by heating the sample from room temperature to T g 2, applying external force to change the original length to L 0 Is elongated to reduce the temperature to T g 1, again applying external force to elongate the length of the sample to L 1 Cooling to room temperature, removing the external force, and recording the length of the remaining part as L 2 (ii) a When the temperature rises to T again g 1, the elongated material shrinks, raising the temperature to T g 2, the material shrinks further, the length at this time is recorded as L 3 . Shape memory fixation rate of L 2 /L 1 (ii) a Shape memory recovery rate of 1- (L) 3 -L 0 )/L 0 . The shape memory recovery rate of the triple shape memory cyanate ester of this example was 93.0%, and the shape memory fixation rate was 97.4%. The deformation process is repeated, and the result of the cycle test is shown in FIG. 5.
The mechanical properties of the triple shape memory cyanate ester tested using the tensile tester were varied, including tensile strength and elongation at break, and the results are shown in fig. 6. As can be seen from the figure, the tensile strength of the triple shape memory cyanate ester of the embodiment is 67.3MPa, the elongation at break is 12.4%, and the triple shape memory cyanate ester has excellent strength and toughness and good mechanical properties.
Example 2
A triple shape memory cyanate ester comprises the following components in parts by weight: 40 parts of cyanate ester prepolymer, 10 parts of bisphenol A epoxy resin, 15 parts of bisphenol A epoxy acrylate, 30 parts of trimethylolpropane triacrylate and 5 parts of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide;
the preparation method comprises the following steps:
s1, preparing printable ink: uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylate and photoinitiator in parts by weight to prepare printable ink;
the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving cyanate ester monomer at 120 ℃, then slowly stirring by magnetic force, uninterruptedly heating and stirring for 192h, and cooling to room temperature;
s2, photocuring, printing and forming: printing and molding the printable ink by adopting a photocuring printer;
s3, constructing an interpenetrating network: and (3) sequentially carrying out ultraviolet irradiation on the printed and molded object for 60min and heating to 180 ℃ for constant temperature treatment for 3h to obtain the triple shape memory cyanate.
The dynamic mechanical analysis of the triple shape memory cyanate prepared in this example is shown in fig. 7, in which the abscissa is temperature, the ordinate on the left side is Storage modulus (Storage modulus), and the ordinate on the right side is mechanical loss (Delta), which shows that the triple shape memory cyanate has two glass transition temperatures, where T is T g 1＝95℃，T g 2 ═ 235 ℃ and no overlap of the two glass transition temperature peaks, indicating excellent triple shape memory performance.
The shape memory performance is characterized, and the shape memory recovery rate of the triple shape memory cyanate ester is 93.8%, and the shape memory fixation rate is 96.1%. The deformation process is repeated, and the result of the cycle test is shown in FIG. 8.
The mechanical properties of the triple shape memory cyanate ester tested using the tensile tester were varied, including tensile strength and elongation at break, and the results are shown in fig. 9. As can be seen from the figure, the tensile strength of the triple shape memory cyanate ester of the embodiment is 69.5MPa, the elongation at break is 10.2%, and the triple shape memory cyanate ester has excellent strength and toughness and good mechanical properties.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A triple shape memory cyanate ester is characterized by comprising the following components in parts by weight: 30-40 parts of cyanate ester prepolymer, 10-20 parts of epoxy resin, 10-20 parts of epoxy acrylate, 20-30 parts of acrylate and 2-5 parts of photoinitiator;
the cyanate ester prepolymer and the epoxy resin are used for forming a thermally initiated polymerization network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymerization network under photo initiation.
2. The ternary shape memory cyanate ester according to claim 1, comprising in parts by weight: 32-38 parts of cyanate ester prepolymer, 12-18 parts of epoxy resin, 14-18 parts of epoxy acrylate, 24-28 parts of acrylate and 3-5 parts of photoinitiator.
3. The ternary shape memory cyanate ester according to claim 2, comprising in parts by weight: 34-36 parts of cyanate ester prepolymer, 16-18 parts of epoxy resin, 16-18 parts of epoxy acrylate, 24-26 parts of acrylate and 4-5 parts of photoinitiator.
4. The triple shape memory cyanate ester according to claim 1, wherein the preparation method of the cyanate ester prepolymer comprises: dissolving a cyanate monomer at the temperature of 110-120 ℃, then continuously heating and stirring for 180-220h, and cooling to room temperature to obtain the cyanate prepolymer.
5. The ternary shape memory cyanate ester according to claim 4, wherein said cyanate ester monomer is bisphenol A cyanate ester.
6. The ternary shape memory cyanate ester according to claim 1, wherein said epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, cyanuric acid epoxy resin, novolac epoxy resin and hydantoin epoxy resin.
7. The ternary shape memory cyanate ester according to claim 1, wherein said epoxy acrylate is selected from one or more of bisphenol a epoxy acrylate, bisphenol F epoxy acrylate, cyanuric epoxy acrylate, novolac epoxy acrylate, and hydantoin epoxy acrylate.
8. The triple shape memory cyanate according to claim 1, wherein the acrylate is selected from one or more of the group consisting of polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.
9. The ternary shape memory cyanate ester according to any of claims 1 to 8, wherein the glass transition temperature of the thermally initiated polymer network is 160-235 ℃ and the glass transition temperature of the photo initiated polymer network is 80-105 ℃.
10. A method for preparing a triple shape memory cyanate ester, which is used for preparing the triple shape memory cyanate ester according to any one of claims 1 to 9, the method comprising the steps of:
s1, uniformly mixing the cyanate ester prepolymer, the epoxy resin, the epoxy acrylate, the acrylate and the photoinitiator in parts by weight to obtain printable ink;
s2, printing and molding the printable ink by adopting a photocuring printing technology;
and S3, sequentially carrying out ultraviolet irradiation and heating treatment on the printed and molded object to obtain the triple shape memory cyanate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN115627071A (en) * | 2022-10-24 | 2023-01-20 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ester ink, preparation method thereof and shape memory cyanate ester material |
| CN116589883A (en) * | 2023-06-20 | 2023-08-15 | 中国科学院兰州化学物理研究所 | Cyanate ester ink, preparation method thereof, cyanate ester shape memory material and application |
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| CN115627071A (en) * | 2022-10-24 | 2023-01-20 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ester ink, preparation method thereof and shape memory cyanate ester material |
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| CN116589883A (en) * | 2023-06-20 | 2023-08-15 | 中国科学院兰州化学物理研究所 | Cyanate ester ink, preparation method thereof, cyanate ester shape memory material and application |
| CN116589883B (en) * | 2023-06-20 | 2024-01-30 | 中国科学院兰州化学物理研究所 | Cyanate ester ink, preparation method thereof, cyanate ester shape memory material and application |
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