CN114806166B - Triple shape memory cyanate and preparation method thereof - Google Patents
Triple shape memory cyanate and preparation method thereof Download PDFInfo
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- CN114806166B CN114806166B CN202210622661.2A CN202210622661A CN114806166B CN 114806166 B CN114806166 B CN 114806166B CN 202210622661 A CN202210622661 A CN 202210622661A CN 114806166 B CN114806166 B CN 114806166B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F283/105—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 on to unsaturated polymers containing more than one epoxy radical per molecule
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- C08L2201/12—Shape memory
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Abstract
The invention provides triple shape memory cyanate and a preparation method thereof, and belongs 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; cyanate ester prepolymers and epoxy resins are used to form thermally initiated polymeric networks upon thermal initiation, and epoxy acrylates and acrylates are used to form photoinitiated polymeric networks upon photoinitiation. The invention forms an interpenetrating network structure by utilizing a thermal initiation polymerization network structure and a photoinitiation polymerization network, and because the reversible phase and the stationary phase of the two network structures are different and the glass transition temperature peak distance is far, the mutual interference of a plurality of shape recovery processes is small, thereby ensuring excellent triple shape memory performance and realizing selective driving deformation and selective shape recovery.
Description
Technical Field
The invention relates to the technical field of shape memory polymer synthesis, in particular to triple shape memory cyanate and a preparation method thereof.
Background
Shape memory polymers (Shape memory polymers, SMPs) are novel smart materials having shape memory ability, i.e., a temporary shape is given to them at a glass transition temperature, and the temporary shape is fixed by cooling, and can be restored to an original shape after being stimulated by the outside, thereby exhibiting a memory function for the original shape. Compared with shape memory alloy and shape memory ceramic, the shape memory polymer has low density, large recoverable deformation, easy processing and forming and changeable deformation temperatureAnd the like, so that the method has wide application prospect in the fields of flexible electronics, biological medicine, aerospace and the like. The shape memory polymer materials developed so far are mainly double shape memory polymers with only one reversible phase and glass transition temperature (Glass transition temperature, T) g ) Only one deformation stage and one recovery stage exist in the shape memory process, and the application of the method has a certain limitation facing the increasingly complex intelligent scene. Therefore, developing new memory storage and implementing multiple shape memories is particularly important to meet the complex needs of future intelligent fields.
Multiple SMPs, such as triple SMPs, can be deformed and fixed from an initial shape to a temporary shape I, then from the temporary shape I to a temporary shape II, etc., to achieve such shape memory characteristics, multiple shape memory polymers need to have two or more glass transition temperatures, and then multiple deformation and recovery stages occur during shape memory, respectively, to perform complex deformation responses. The complex shape memory effect makes multiple shape memory polymers possible to use in many fields. Triple SMPs reported to date are generally prepared by blending two resins or by polymer grafting. When preparing triple SMPs by blending two resins, the two resins need to have good compatibility, and the curing mode is single and is generally thermosetting, which greatly limits the types of optional resins. When the SMPs are prepared by polymer grafting, the preparation method is complicated, and the 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 glass transition peak separation is not obvious, and the shape recovery of two temporary shapes mutually interfere, thereby being unfavorable for subsequent application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a triple shape memory cyanate and a preparation method thereof.
In order to achieve the above purpose, the present invention is specifically realized by the following technical scheme:
the invention provides a triple shape memory cyanate, 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 polymeric network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymeric network under photo initiation.
Further, the triple shape memory cyanate 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, the method includes: 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: and dissolving the cyanate monomer at 110-120 ℃, then continuously heating and stirring for 180-220 hours, and cooling to room temperature to obtain the cyanate prepolymer.
Further, the cyanate monomer is bisphenol a cyanate.
Further, the epoxy resin is selected from one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, cyanuric acid epoxy resin, phenolic 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, phenolic epoxy acrylate and hydantoin epoxy acrylate.
Further, the acrylic acid ester 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-diphenyl phosphine oxide.
Further, the glass transition temperature of the thermally initiated polymeric network is 160-235 ℃, and the glass transition temperature of the photo-initiated polymeric network is 80-105 ℃.
In addition, the invention provides a preparation method of the triple shape memory cyanate, which comprises the following steps:
s1, uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylic ester and photoinitiator according to parts by weight to prepare printable ink;
s2, printing and forming the printable ink by adopting a photo-curing printing technology;
and S3, sequentially carrying out ultraviolet irradiation and heating treatment on the printed and formed object to obtain the triple shape memory cyanate.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the cyanate prepolymer and the epoxy resin are utilized to generate a thermal initiation polymerization network structure through polymerization reaction under thermal initiation, the epoxy acrylate and the acrylate are utilized to generate a photoinitiation polymerization network through polymerization reaction under photoinitiation, the thermal initiation polymerization network structure and the photoinitiation polymerization network are mutually inserted to form an interpenetrating network, and as the reversible phase and the stationary phase of the thermal initiation polymerization network and the photoinitiation polymerization network are different, the glass transition temperature range of the resin is wider and the glass transition temperature peak distance is far, so that the mutual interference of a plurality of 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. In addition, the interpenetrating network is constructed by different resin types and different curing modes, so that the polymer has more flexible design and more excellent performance.
2. The invention is beneficial to enhancing mechanical property by forming an interpenetrating network structure through the thermal initiation polymerization network and the photoinitiation polymerization network, the tensile strength of the triple shape memory cyanate is up to more than 60MPa, the elongation at break is more than 10%, the shape memory fixation 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 of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing the morphology of cyanate ester prepolymer at different heating times according to the embodiment of the present invention;
FIG. 2 is a graph of dynamic mechanical analysis of a triple shape memory cyanate of example 1 of the present invention;
FIG. 3 is a representation of the triple shape memory deformation process of the triple shape memory cyanate of example 1 of the present invention;
FIG. 4 is a representation of the triple shape memory recovery process of the triple shape memory cyanate of example 1 of the present invention;
FIG. 5 is a graph of a shape memory cycle test of a ternary shape memory cyanate ester of example 1 of the present invention;
FIG. 6 is a graph showing the mechanical properties of the ternary shape memory cyanate ester of example 1 of the present invention;
FIG. 7 is a graph of dynamic mechanical analysis of a triple shape memory cyanate of example 2 of the present invention;
FIG. 8 is a graph of a shape memory cycle test of a ternary shape memory cyanate ester of example 2 of the present invention;
FIG. 9 is a graph showing the mechanical properties of the ternary shape memory cyanate ester of example 2 of the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. In addition, the terms "comprising," "including," "having," and "containing" are not limiting, as other steps and other ingredients may be added that do not affect the result. Materials, equipment, reagents are commercially available unless otherwise specified.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present invention are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained. 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 that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The embodiment of the invention provides a triple shape memory cyanate, 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 polymeric network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photo initiated polymeric network under photo initiation.
In the invention, the cyanate ester prepolymer is a main material of thermal initiation polymerization, and can generate self-polymerization reaction when the cyanate ester is heated to generate triazine ring network crosslinking points, but the generated 1,3, 5-triazine ring structure is highly symmetrical, and has poor brittleness and toughness. The epoxy resin is used as a modifier of cyanate and is used for modifying the cyanate network structure, so that the crosslinking degree of triazine rings is reduced, and the toughness of the epoxy resin is enhanced. Therefore, the cyanate ester prepolymer and the epoxy resin are subjected to polymerization reaction under the thermal initiation to generate a thermal initiation polymerization network structure with good shape memory performance. Both epoxy acrylate and acrylic ester contain allyl active groups, are main materials for photoinitiated polymerization, and under the irradiation of ultraviolet light, the photoinitiator generates active free radicals to induce polymerization reaction. Because acrylic ester and epoxy acrylic ester are small molecular substances, when the acrylic ester and the epoxy acrylic ester are respectively and independently polymerized into a network structure, the network structure unit is single, which leads to regular and compact network structure and extremely poor toughness, and is unfavorable for shape memory performance. Therefore, the epoxy acrylate and the acrylic ester are matched according to a certain proportion, and polymerization reaction occurs under photoinitiation, so that an irregular photoinitiated polymerization network structure is formed, and the mechanical property of the photoinitiated polymerization network structure is improved. In addition, the acrylic ester can also be used as a micromolecular reactive diluent for adjusting the viscosity of the ink and enhancing the printability of the ink and the matching property with a photo-curing printer.
Shape memory performance depends on the polymer molecular network structure in which network crosslinks are stationary phases and molecular segments between crosslinks 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 fixed in shape; and heating to the glass transition temperature again, retracting the molecular chains, and dragging the crosslinking points to return to the original state, wherein the macroscopic appearance is shape recovery. The thermal initiation polymerization network and the photoinitiation polymerization network generated by the invention have different molecular structures and thermodynamic properties, specifically, the reversible phases and the stationary phases of the two network structures are different, and 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 photoinitiation polymerization network formed by the epoxy acrylate and the acrylic ester has low strength and low glass transition temperature; the glass transition temperature peaks of the two network structures are far away, so that mutual interference of multiple shape recovery processes is small, excellent triple shape memory performance is ensured, and selective driving deformation and selective shape recovery can be realized. The interpenetrating network is constructed by different resin types and different curing modes, so that the polymer has more flexible design and more excellent performance. In addition, the thermal initiation polymerization network and the photoinitiation polymerization network form an interpenetrating network structure, the interpenetration of the two network structures also has a synergistic effect on the mechanical properties of the resin, the tensile strength of the triple shape memory cyanate is up to more than 60MPa, the elongation at break is more than 10%, the shape memory fixation rate is more than 96%, and the shape memory recovery rate is more than 93%.
The glass transition temperature of the thermally initiated polymerization network is 160-235 ℃ and the glass transition temperature of the photoinitiated polymerization network is 80-105 ℃.
The larger the difference between the glass transition temperatures of the two network structures, the farther the two glass transition temperature peaks are from each other, the smaller the mutual interference between the two shape recovery is, and the better the triple shape memory performance is. When the addition amount of the epoxy resin is too high, the generation amount of triazine ring is greatly reduced, the strength of the thermal-initiated polymerization network is reduced, and the glass transition temperature is reduced. The epoxy acrylate and the acrylic ester form a photoinitiated polymerization network, when the addition amount of the acrylic ester is too high, the brittleness of the network structure is large, the mechanical property is poor, and the glass transition temperature is slightly increased. In the foregoing cases, the distance between two glass transition temperature peaks becomes smaller, and overlapping of glass transition temperature ranges occurs, which is unfavorable for triple shape memory performance. Thus, preferably, the triple shape memory cyanate comprises, 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, the method 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: and dissolving the cyanate monomer at 110-120 ℃, then continuously heating and stirring for 180-220 hours, 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, phenolic 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, phenolic 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-diphenyl phosphine oxide, and the photoinitiator can generate active free radicals to induce acrylic esters to generate polymerization reaction under ultraviolet light irradiation.
Another embodiment of the present invention provides a method for preparing the triple shape memory cyanate as described above, comprising the steps of:
s1, preparing printable ink: uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylic ester and photoinitiator according to parts by weight to prepare printable ink;
s2, photo-curing, printing and forming: printing and forming the printable ink by adopting a photo-curing printing technology;
s3, constructing an interpenetrating network: and sequentially carrying out ultraviolet irradiation and heating treatment on the printed and formed object to obtain the triple shape memory cyanate.
The preparation method of the ternary shape memory cyanate is the same as that of the ternary shape memory cyanate in the prior art, and the preparation method is not repeated here. The invention adopts a photo-curing printing combined photo-thermal dual-stage curing method, the photo-curing printing can realize the integrated rapid forming of a complex structure and the preliminary forming of a photoinitiated polymerization network structure, and then ultraviolet light irradiation is adopted to carry out photo-post curing so as to improve the printing efficiency and strengthen the photoinitiated polymerization network structure. Finally, heating treatment and solidification are carried out to further improve the mechanical property of the material and generate high T g Is a thermally initiated polymeric network structure with increased double T g The difference between the two is favorable for improving the triple shape memory performance.
Internal stress is generated when the heat treatment is used for curing, and the influence of the internal stress is weakened by pre-curing. Specifically, the pre-curing treatment adopts a gradient heating mode, and comprises the following steps: the temperature is kept at 150 ℃ for 3 hours and at 180 ℃ for 3 hours, the temperature of rapid curing and crosslinking of cyanate is above 210 ℃, the rapid curing and crosslinking reaction is carried out at 150 ℃ and 180 ℃, the activity of molecular chains at high temperature is high, and the cyanate can be adjusted to a position with low internal stress, so that the influence caused by the internal stress is relieved.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, which do not address specific conditions in the following examples, are generally in accordance with the conditions recommended by the manufacturer.
Example 1
The triple shape memory cyanate 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, acrylic ester and photoinitiator according to parts by weight to prepare printable ink;
the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving the cyanate monomer at 120 ℃, then slowly stirring by magnetic force, continuously heating and stirring for 192h, and cooling to room temperature;
s2, photo-curing, printing and forming: printing and forming printable ink by using a photo-curing printer, and printing to obtain a six-petal flower structure in the example;
s3, constructing an interpenetrating network: and sequentially carrying out ultraviolet irradiation on the printed and formed object for 60min, and heating to 180 ℃ for 3h at constant temperature to obtain the triple shape memory cyanate.
The results of dynamic mechanical analysis of the ternary shape memory cyanate prepared in this example are shown in FIG. 2, in which the abscissa indicates temperature, the left ordinate indicates Storage modulus (Storage modulus), and the right ordinate indicates mechanical loss (Tan Delta), and the ternary shape memory cyanate has two glass transition temperatures, where T g 1＝102℃，T g 2=202 ℃, and the two glass transition temperature peaks are significantly separated and the ranges overlap less, indicating that they have excellent triple shape memory properties.
The triple shape memory deformation process is exemplified as follows: heating triple shape memory cyanate to T g 2 temperatureApplying external force to deform 1,3,5 petals, or one or two or more other petals, and cooling to T g At 2 temperature and T g And at a temperature above 1 ℃, external force is applied to deform the petals 2,4 and 6 (see figure 3). At T g Petals (2, 4, 6) deformed at 1 temperature can be at T g Shape recovery above 1 temperature, also at T g 2 to recover shape above temperature, at T g Petals (1, 3, 5) deformed above 2 ℃ can only be at T g Above 2 f, the shape returns (see fig. 4), whereby selective deformation and selective shape return can be achieved.
In addition, the shape memory performance was characterized by heating the sample from room temperature to T g 2, applying external force to make the original length L 0 Is stretched and the temperature is reduced to T g 1, applying external force again to elongate the sample length to L 1 Cooling to room temperature, removing external force, and keeping the length L 2 The method comprises the steps of carrying out a first treatment on the surface of the When the temperature rises again to T g 1, the elongated material contracts and the temperature is raised to T g 2, the material further shrinks, the length at this time being denoted L 3 . Shape memory fixation rate=l 2 /L 1 The method comprises the steps of carrying out a first treatment on the surface of the Shape memory recovery = 1- (L) 3 -L 0 )/L 0 . The triple shape memory cyanate of this example had a shape memory recovery of 93.0% and a shape memory fixation of 97.4%. The deformation process is cycled, and the cycling test results are shown in FIG. 5.
The change in mechanical properties of the triple shape memory cyanate, including tensile strength and elongation at break, tested using a tensile tester is shown in figure 6. As can be seen from the graph, the triple shape memory cyanate of the embodiment has the tensile strength of 67.3MPa and the elongation at break of 12.4 percent, and has excellent strength and toughness and good mechanical property.
Example 2
The triple shape memory cyanate 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-diphenyl phosphine oxide;
the preparation method comprises the following steps:
s1, preparing printable ink: uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylic ester and photoinitiator according to parts by weight to prepare printable ink;
the preparation method of the cyanate ester prepolymer comprises the following steps: dissolving the cyanate monomer at 120 ℃, then slowly stirring by magnetic force, continuously heating and stirring for 192h, and cooling to room temperature;
s2, photo-curing, printing and forming: printing and forming printable ink by using a photo-curing printer;
s3, constructing an interpenetrating network: and sequentially carrying out ultraviolet irradiation on the printed and formed object for 60min, and heating to 180 ℃ for 3h at constant temperature to obtain the triple shape memory cyanate.
The results of dynamic mechanical analysis of the ternary shape memory cyanate prepared in this example are shown in FIG. 7, in which the abscissa indicates temperature, the left ordinate indicates Storage modulus (Storage modulus), and the right ordinate indicates mechanical loss (Delta), and the ternary shape memory cyanate has two glass transition temperatures, T g 1＝95℃，T g 2=235 ℃, and the two glass transition temperature peaks do not overlap, indicating that it has excellent triple shape memory properties.
Characterization of shape memory performance the triple shape memory cyanate of this example had a shape memory recovery of 93.8% and a shape memory fixation of 96.1%. The deformation process is cycled, and the cycling test results are shown in FIG. 8.
The change in mechanical properties of the triple shape memory cyanate, including tensile strength and elongation at break, tested using a tensile tester is shown in fig. 9. As can be seen from the graph, the triple shape memory cyanate of the embodiment has the tensile strength of 69.5MPa and the elongation at break of 10.2 percent, and has excellent strength and toughness and good mechanical property.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.
Claims (6)
1. The triple shape memory cyanate 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 thermal initiation polymerization network under thermal initiation, and the epoxy acrylate and the acrylate are used for forming a photoinitiation polymerization network under photoinitiation; the cyanate monomer is bisphenol A cyanate, the epoxy resin is bisphenol A epoxy resin, the epoxy acrylate is bisphenol A epoxy acrylate, and the acrylate is one of polyethylene glycol diacrylate and trimethylolpropane triacrylate.
2. The triple shape memory cyanate as set forth in 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 triple shape memory cyanate as set forth in 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 of claim 1, wherein the preparation method of the cyanate prepolymer comprises: and dissolving the cyanate monomer at 110-120 ℃, then continuously heating and stirring for 180-220 hours, and cooling to room temperature to obtain the cyanate prepolymer.
5. The triple shape memory cyanate of any of claims 1-4, wherein the thermally induced polymeric network has a glass transition temperature of 160-235 ℃ and the photoinitiated polymeric network has a glass transition temperature of 80-105 ℃.
6. A method of preparing a triple shape memory cyanate, for use in preparing a triple shape memory cyanate as claimed in any one of claims 1-5, comprising the steps of:
s1, uniformly mixing cyanate ester prepolymer, epoxy resin, epoxy acrylate, acrylic ester and photoinitiator according to parts by weight to prepare printable ink;
s2, printing and forming the printable ink by adopting a photo-curing printing technology;
and S3, sequentially carrying out ultraviolet irradiation and heating treatment on the printed and formed object to obtain the triple shape memory cyanate.
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| CN115627071B (en) * | 2022-10-24 | 2023-11-24 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ink, preparation method thereof and shape memory cyanate material |
| 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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| CN113087852A (en) * | 2021-04-26 | 2021-07-09 | 中国科学院兰州化学物理研究所 | Cyanate ester shape memory polymer material capable of being printed in 4D mode, preparation method of cyanate ester shape memory polymer material, cyanate ester shape memory polymer device and application of cyanate ester shape memory polymer device |
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