CN113683770B - Polyaryletherketone with multiple shape memory effect, preparation and application thereof - Google Patents

Polyaryletherketone with multiple shape memory effect, preparation and application thereof Download PDF

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CN113683770B
CN113683770B CN202111011711.5A CN202111011711A CN113683770B CN 113683770 B CN113683770 B CN 113683770B CN 202111011711 A CN202111011711 A CN 202111011711A CN 113683770 B CN113683770 B CN 113683770B
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polyaryletherketone
shape memory
blend
multiple shape
difluorobenzophenone
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CN113683770A (en
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冷劲松
杨帅
何阳
刘彦菊
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4031—(I) or (II) containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
    • C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • C08L2201/00—Properties
    • C08L2201/12—Shape memory
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention relates to shape memory polyaryletherketone, and in particular discloses polyaryletherketone with multiple shape memory effects, a preparation method and an application thereof. The invention also discloses the polyaryletherketone and a film prepared from the polyaryletherketone blend. The shape memory polyaryletherketone provided by the invention has wide raw materials, can realize multiple shape memory effects, has good shape fixation rate, high shape recovery rate and higher shape recovery rate for the first time in the shape memory polyaryletherketone polymer, and has potential application value in the fields of aerospace, biomedical and flexible devices.

Description

Polyaryletherketone with multiple shape memory effect, preparation and application thereof
Technical Field
The invention relates to the technical field of shape memory materials, in particular to polyaryletherketone with multiple shape memory effects, a preparation method and application thereof.
Background
In nature, various stimulus responses and deformation phenomena exist, such as rotation of sunflowers towards the sun, color-changing camouflage of chameleon and the like. Inspired by the nature, intelligent materials capable of spontaneously responding to external stimuli are widely paid attention to by scientists. Because of its inherent stimulus response capability and shape deformation capability, stimulus responsive materials are widely used in the fields of space construction, bioengineering, flexible robots, smart devices, and the like. The shape memory polymer has the advantages of unique shape memory property, excellent processability, light weight, low cost and the like, and is widely applied to space structures, bionic devices, artificial tissues and the like.
The combination of different stimulus patterns imparts multiple stimulus response patterns to the shape memory polymer. In general, the stimulus response patterns of shape memory polymers are diverse, including thermal, optical, electrical, magnetic, acoustic, and solvent. Most conventional shape memory polymers are thermotropic shape memory polymers and can be applied to thermotropic shape memory composites. As for other stimulus response modes, such as optical, electrical, and magnetic responses, etc., can be achieved by incorporating sensitive stimulus responsive functional fillers into the composite. Due to the unique stimulus response behavior, the multiple shape memory polymer has wide application prospect in the field of the multiprogramming intelligent device.
Currently, multiple shape memory polymers are mostly elastomeric or low transition temperature flexible polymers. The multiple shape memory materials have generally poor mechanical strength and slow recovery speed, and greatly limit the application of the multiple shape memory materials in the field of intelligent structural devices. Thus, in order to ensure diverse stimulus response patterns and multiple deformability, shape memory polymer materials need more excellent mechanical strength and stability. Polyaryletherketone is used as a semi-crystalline linear thermoplastic polymer, has excellent mechanical property and thermal stability, is a polymer material with excellent performance, but the shape memory polyaryletherketone only has double shape memory effect and no multiple shape memory capability, so that development of a multiple shape memory material based on the polyaryletherketone is urgently needed.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of polyaryletherketone with multiple shape memory effect, which aims to solve the problems that most of polymers with multiple shape memory effect in the prior art are elastic bodies, the mechanical strength and stability are poor, the application of the polyaryletherketone in the fields of aerospace, biomedical and flexible devices is limited, and the shape memory polyaryletherketone only has the double shape memory effect and has no multiple shape memory capability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a shape memory polyaryletherketone having a structure represented by formula (I):
Wherein n is an integer from 80 to 240, x+y=1, x is more than or equal to 0, y is more than or equal to 0, and the molecular weight of the shape memory polyaryletherketone is 45-90kg/mol.
In certain specific embodiments, n is 80, 90, 100, 150, 200, 240 or any integer therebetween; x is 0, 0.1, 0.3, 0.5, 0.7, 0.8, 0.9, 1.0 or any number therebetween.
Further, the shape memory polyaryletherketone is prepared by polymerization reaction of bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone; the mole ratio of bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone monomer is x: (1-x): 1, and x is more than or equal to 0 and less than or equal to 1.
Further, the glass transition temperature of the shape memory polyaryletherketone is positively correlated with the x value in the formula (1).
In the technical scheme of the invention, the glass transition temperature of the polyaryletherketone with the structure shown in the formula (I) is increased along with the increase of the x value.
The second aspect of the invention provides a preparation method of the shape memory polyaryletherketone, which comprises the following steps:
step S1, mixing bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone in proportion, and then uniformly mixing with a salifying agent, a solvent and a water-carrying agent to form a reaction system;
step S2, heating the reaction system to 130-150 ℃ and performing azeotropic reflux;
Step S3, continuously heating to 160-190 ℃ to react to obtain a crude polyaryletherketone product;
And S4, respectively using distilled water and ethanol to obtain a crude product of the polyaryletherketone obtained in the step S3, and drying to obtain the shape memory polyaryletherketone.
Further, in step S1, the salt former is selected from potassium carbonate or sodium carbonate, the solvent is selected from any one of sulfolane, N-methylpyrrolidone, N '-dimethylformamide and N, N' -dimethylacetamide, and the water-carrying agent is toluene.
Further, in the step S1, the mol ratio of the salifying agent to the 4,4' -difluorobenzophenone is 1:1-1.2; the solid content of the reaction system is 20% -30%; the volume of the water-carrying agent is 50% of that of the solvent.
Preferably, in the step S2, the azeotropic reflux time is 2-4 hours;
Preferably, in the step S3, the reaction time for continuously heating is 3-5 hours;
preferably, in step S4, the drying is vacuum oven drying at 60-80 ℃.
In the technical scheme of the invention, the solid content of the reaction system is the ratio of the total mass of bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4 '-difluorobenzophenone in the reaction system to the sum of the masses of bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone and the solvent.
In a third aspect, the present invention provides a multiple shape memory polyaryletherketone blend, obtained by physically blending different polyaryletherketones having the structure of formula (I):
wherein n is an integer from 80 to 240, x+y=1, x is not less than 0, y is not less than 0, and the molecular weight is 45 to 90kg/mol.
Further, the different polyaryletherketones are polyaryletherketones with different glass transition temperatures, and the difference between the different glass transition temperatures is more than or equal to 7 ℃;
further, the blending is an equal mass blending;
Preferably, two different polyaryletherketones having the structure of formula (I) are physically blended, the multiple shape memory being a triple shape memory; three different polyaryletherketones having the structure of formula (I) are physically blended, the multiple shape memory being a quadruple shape memory.
In a fourth aspect, the present invention provides the use of a shape memory polyaryletherketone as described above or a multiple shape memory polyaryletherketone blend as described above in the field of shape memory materials.
In a fifth aspect, the present invention provides a shape memory polyaryletherketone film prepared from the shape memory polyaryletherketone described above or the multiple shape memory polyaryletherketone blend described above.
The technical scheme has the following advantages or beneficial effects:
The invention prepares the polyaryletherketone with double shape memory effect by polymerizing bisphenol AF, 2-di (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone, regulates and controls the glass transition temperature of the polyaryletherketone by changing the proportion of reaction monomers, and endows the polyaryletherketone blend with multiple shape memory effect by blending the polyaryletherketone with different glass transition temperatures. Compared with the prior art, the polyaryletherketone blend provided by the invention has multiple memory effect, can realize triple and quadruple shape memory recovery, has good mechanical property and easy processing and forming due to the rigidity group and the flexibility of the molecular chain in the molecular structure compared with the multiple shape memory material of the elastic body and the flexible polymer with low transition temperature in the prior art, has the multiple shape memory effect, has the advantages of good shape fixation rate, high shape recovery rate and higher shape recovery rate for the first time in the shape memory polyaryletherketone polymer, and has potential application value in the fields of aerospace, biomedical and flexible devices. Has potential application value in the fields of aerospace, biomedical and flexible devices.
Drawings
FIG. 1 is a graph showing the glass transition temperatures of the poly (arylene ether ketone) s of examples 1, 2, 4 and the poly (arylene ether ketone) s of examples 6, 12 according to the present invention;
FIG. 2 is a graph showing the four-fold shape memory effect of the film sample of the multiple shape memory polyaryletherketone blend in example 12 of the present invention.
Detailed Description
The following examples are only some, but not all, of the examples of the invention. Accordingly, the detailed description of the embodiments of the invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
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 description of the term "certain embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same implementations or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
One of the purposes of the present invention is to design a polyaryletherketone with shape memory, and in the following embodiments, the preparation method thereof comprises the following steps:
Step S1, reacting bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -difluorobenzophenone and a salifying agent;
step S2, heating the reaction system to azeotropic reflux of the water carrying agent and water in an N 2 atmosphere, and reacting for 4 hours;
Step S3, continuously heating to 160-190 ℃, finishing the reaction after 5 hours of reaction, and pouring the polymerization reaction product into distilled water to obtain a crude polyaryletherketone product;
And S4, washing the crude product of the polyaryletherketone by distilled water and ethanol respectively, and drying in a vacuum oven at 60-80 ℃ to obtain the shape memory polyaryletherketone.
In the step S2, azeotropic reflux is realized between the water-carrying agent and water in the reaction system by heating, and the water generated in the reaction process is separated from the reaction system.
In the examples below, the molecular weight of the polyaryletherketone is 45-90kg/mol.
It is another object of the present invention to provide a multiple shape memory polyaryletherketone blend, in which the multiple shape memory polyaryletherketone blend is prepared by physically blending a shape memory polyaryletherketone having a non-transition temperature.
Example 1: polyaryletherketone P1
In this embodiment, the polyaryletherketone P1 has a structure represented by formula (II):
Wherein n has a value ranging from 120 to 240 and a glass transition temperature of 120.9 ℃ (see figure 1).
In the polymerization reaction: the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the 4', 4-difluorobenzophenone and the potassium carbonate is 3.6626:2.182:1.3821.
The total mass of the solid contents, i.e., 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4 '4-difluorobenzophenone, was 20% of the total mass of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' 4-difluorobenzophenone and sulfolane.
Toluene was 50% by volume of sulfolane.
The preparation process comprises the following steps:
in the step S3, continuously heating to 190 ℃;
in step S4, the mixture is dried in a vacuum oven at 80 ℃.
Example 2: polyaryletherketone P2
In this embodiment, the polyaryletherketone P2 has a structure represented by formula (III):
wherein n has a value in the range of 75-150 and a glass transition temperature of 138.5deg.C (see FIG. 1).
In the polymerization reaction: the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the bisphenol AF, the 4', 4-difluorobenzophenone and the potassium carbonate is 3.6626:3.3623:4.364:2.7642.
The total mass of the solid contents, i.e., 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF, 4 '4-difluorobenzophenone, was 20% of the total mass of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF, 4' 4-difluorobenzophenone and sulfolane.
Toluene was 50% by volume of sulfolane.
The preparation process comprises the following steps:
in the step S3, continuously heating to 190 ℃;
in step S4, the mixture is dried in a vacuum oven at 80 ℃.
Example 3: polyaryletherketone P2-2
In this embodiment, the polyaryletherketone P2 has a structure represented by formula (IV):
wherein, the value range of n is 75-150, and the glass transition temperature is 141.6 ℃.
In the polymerization reaction: the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the bisphenol AF, the 4', 4-difluorobenzophenone and the potassium carbonate is 1.8313:6.7246:4.364:2.7642.
The total mass of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF and 4 '4-difluorobenzophenone, which were the solid contents, was 20% of the total mass of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF, 4' 4-difluorobenzophenone and sulfolane.
Toluene was 50% by volume of sulfolane.
The preparation process comprises the following steps:
in the step S3, continuously heating to 190 ℃;
in step S4, the mixture is dried in a vacuum oven at 80 ℃.
Example 4: polyaryletherketone P3
In this embodiment, the polyaryletherketone P3 has a structure represented by formula (V):
wherein n has a value ranging from 80 to 240 and a glass transition temperature of 147.7 ℃ (see figure 1).
In the polymerization reaction: the mass ratio of bisphenol AF, 4' 4-difluorobenzophenone and potassium carbonate is 3.3623:2.182: 1.3821.
The total mass of the solid content, namely bisphenol AF, 4 '4-difluorobenzophenone, is 20% of the total mass of bisphenol AF, 4' 4-difluorobenzophenone and sulfolane.
Toluene was 50% by volume of sulfolane.
The preparation process comprises the following steps:
in the step S3, continuously heating to 190 ℃;
in step S4, the mixture is dried in a vacuum oven at 80 ℃.
Example 5: polyaryletherketone P2-1
In this embodiment, the polyaryletherketone P2-1 has a structure represented by formula (VI):
Wherein, the value range of n is 75-150, and the glass transition temperature is 124.2 ℃.
In the polymerization reaction: the mass ratio of the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the bisphenol AF, the 4', 4-difluorobenzophenone and the potassium carbonate is 7.3252:1.6812:4.364:2.7642.
The total mass of the solid contents, i.e., 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF, 4 '4-difluorobenzophenone, was 20% of the total mass of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bisphenol AF, 4' 4-difluorobenzophenone and sulfolane.
Toluene was 50% by volume of sulfolane.
The preparation process comprises the following steps:
step S3, continuously heating to 190 ℃;
And S4, drying in a vacuum oven at 80 ℃.
Example 6: PAEK-2 as poly (arylene ether ketone) blend
Polyaryletherketone P1 and polyaryletherketone P2 are mixed according to the mass ratio of 1: and (3) carrying out physical blending according to the proportion of 1 to obtain the PAEK blend PAEK-2 with triple memory effect. In this example, the glass transition temperature of PAEK-2 is Tg 1：113.7℃;Tg2: 143.3 ℃ (see figure 1).
Example 7:
The poly (arylene ether ketone) P1 and poly (arylene ether ketone) P2-2 are mixed according to the mass ratio of 1:1 to obtain the polyaryletherketone blend with triple memory effect.
Example 8:
Polyaryletherketone P1 and polyaryletherketone P3 are mixed according to the mass ratio of 1:1 to obtain the polyaryletherketone blend with triple memory effect.
Example 9:
The poly (arylene ether ketone) P2-1 and poly (arylene ether ketone) P2-2 are mixed according to the mass ratio of 1:1 to obtain the polyaryletherketone blend with triple memory effect.
Example 10:
Polyaryletherketone P2-1 and polyaryletherketone P3 are mixed according to the mass ratio of 1:1 to obtain the polyaryletherketone blend with triple memory effect.
Example 11
Polyaryletherketone P2 and polyaryletherketone P3 are mixed according to the mass ratio of 1:1 to obtain the polyaryletherketone blend with triple memory effect.
Example 12: PAEK-3 as poly (arylene ether ketone) blend
Polyaryletherketone P1, polyaryletherketone P2 and polyaryletherketone P3 are mixed according to the mass ratio of 1:1: and (3) carrying out physical blending according to the proportion of 1 to obtain the polyaryletherketone blend PAEK-3 with the quadruple memory effect. In this example, the glass transition temperature of PAEK-3 is: tg 1：108.9℃;Tg2：133.9℃;Tg3: 156.3C (see FIG. 1).
In this example, the PAEK-3 has a heat resistance temperature of 350℃and a Young's modulus of 1.1GPa.
In order to perform performance test on the polyaryletherketone in the present invention, the polyaryletherketone blend prepared by the method in the above example 6 to example 12 is prepared into a film, and the specific method is as follows: dissolving the polyaryletherketone blend in the embodiment 6-12 in N-methyl pyrrolidone to prepare a polyaryletherketone solution with the concentration of 15%, pouring the prepared solution into a prepared mold, and vacuum drying at 80 ℃ for 48 hours to ensure that the solvent is completely volatilized to obtain the polyaryletherketone blend film.
The method is characterized in that the multiple shape memory performance of the shape memory polyaryletherketone prepared by the method in the embodiment is characterized after the shape memory polyaryletherketone is prepared into a film, and comprises the following steps:
Preparing the polyaryletherketone or the polyaryletherketone blend in the above examples 1-12 into a film, and cutting the film into rectangular samples with the thickness of 25X 5mm 2; selecting a certain temperature near the corresponding Tg temperature, giving a temporary shape to the rectangular sample, keeping the temporary shape to be cooled, and raising the temperature again, wherein the raised temperature is a preset transition temperature, and recording the shape recovery process of the polyaryletherketone film sample.
As shown in FIG. 2, the film sample of the polyaryletherketone blend in example 12, which had an initial shape I of a bar, was deformed into a shape II with one end folded by applying an external force to the film sample of the initial shape I at 160℃and maintained for 1min at 140℃to fix the shape. And under the temperature condition of 140 ℃, giving an external force to the container to obtain a shape III with two folded ends, and maintaining the external force at the temperature of 120 ℃ for 1min to fix the shape. Under the temperature condition of 120 ℃, the external force is exerted, and obtaining a temporary shape IV folded at two ends after being folded, and keeping the external force to reduce the temperature so as to fix the shape. Then, the sample of temporary shape IV was heated again to 120 ℃ and was seen to undergo spontaneous shape recovery behavior from temporary shape IV to shape III. At this point, the temperature was raised to 140 ℃, and the sample returned from shape III to shape II. Then, the temperature was raised to 160 ℃, and the film sample was observed to return from shape II to the original shape I. In this embodiment, the shape recovery rate is within 10s, and the shape fixation rate is greater than 98%. And between the temperatures of T g1、Tg2 and T g3, the polymer molecular chain segments are enabled to move through temperature rise, so that the entropy of the polymer molecular chain segments is increased, macroscopic shape recovery behaviors of the PAEK-3 polymer at the temperatures of T g1、Tg2 and T g3 are promoted, and the quadruple shape memory effect of the PAEK-3 polymer is realized.
Therefore, the shape memory polyaryletherketone with multiple shape memory effects can realize multiple shape memory effects at different transition temperatures.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent changes made by the specification and drawings of the present invention, or direct or indirect application in other related technical fields, are included in the scope of the present invention.

Claims (13)

1. The multiple shape memory polyaryletherketone blend is characterized in that the multiple shape memory polyaryletherketone blend is obtained by physically blending different polyaryletherketones with a structure shown in a formula (I),
Wherein n is an integer from 80 to 240, x+y=1, x is not less than 0, y is not less than 0, and the molecular weight is 45 to 90kg/mol.
2. The multi-shape memory polyaryletherketone blend according to claim 1, wherein the polyaryletherketone of the structure represented by formula (I) is prepared by polymerizing bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone; the molar ratio of bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone monomer is (1-x): x:1, and x is more than or equal to 0 and less than or equal to 1.
3. The multiple shape memory polyaryletherketone blend of claim 1, wherein the method of preparing the polyaryletherketone of the structure of formula (I) comprises the steps of:
step S1, mixing bisphenol AF, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4' -difluorobenzophenone in proportion, and then uniformly mixing with a salifying agent, a solvent and a water-carrying agent to form a reaction system;
step S2, heating the reaction system to 130-150 ℃ and performing azeotropic reflux;
step S3, continuously heating to 160-190 ℃ for reaction to obtain a crude polyaryletherketone product;
And S4, washing the crude product of the polyaryletherketone obtained in the step S3 with distilled water and ethanol respectively, and drying to obtain the polyaryletherketone with the structure shown in the formula (I).
4. A multiple shape memory polyaryletherketone blend according to claim 3, wherein in step S1, the salt former is selected from potassium carbonate or sodium carbonate, the solvent is selected from any one of sulfolane, N-methylpyrrolidone, N '-dimethylformamide and N, N' -dimethylacetamide, and the water-carrying agent is toluene.
5. The multiple shape memory polyaryletherketone blend according to claim 3, wherein in step S1, the molar ratio of the salifying agent to 4,4' -difluorobenzophenone is 1:1-1.2, the solid content of the reaction system is 20% -30%, and the volume of the water-carrying agent is 50% of the solvent.
6. The multiple shape memory polyaryletherketone blend according to claim 3, wherein in step S2, the azeotropic reflux time is 2h to 4h.
7. The poly shape memory polyaryletherketone blend according to claim 3, wherein in step S3, the reaction time is continued to be raised for 3 to 5 hours.
8. A multiple shape memory polyaryletherketone blend according to claim 3, wherein in step S4, the drying is a 60-80 ℃ vacuum oven drying.
9. The multiple shape memory polyaryletherketone blend of claim 1, wherein the different polyaryletherketones are polyaryletherketones having different glass transition temperatures, the different glass transition temperatures being a difference in glass transition temperatures of ≡7 ℃.
10. The multiple shape memory polyaryletherketone blend according to claim 1, wherein the blend is an equal mass blend.
11. The multiple shape memory polyaryletherketone blend of claim 9, wherein two different polyaryletherketones having the structure of formula (I) are physically blended, the multiple shape memory being a triple shape memory; three different polyaryletherketones having the structure of formula (I) are physically blended, the multiple shape memory being a quadruple shape memory.
12. Use of a multiple shape memory polyaryletherketone blend according to any one of claims 1 to 11 in the field of shape memory materials.
13. A shape memory polyaryletherketone film prepared from the multiple shape memory polyaryletherketone blend according to any one of claims 1 to 11.
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